Warm skin-friendly fabric and preparation method thereof

Abstract

The invention discloses a warm skin-friendly fabric and a preparation method thereof, and relates to the field of fabrics. When preparing the warm skin-friendly fabric, the present invention reacts polyacrylonitrile powder, glycidyl acrylate and dimethyl allyl phosphate to obtain pre-modified polyacrylonitrile; then the pre-modified polyacrylonitrile is sequentially reacted with 3-amino-1,2-propylene glycol and dicyandiamide to obtain functionalized polyacrylonitrile; after the kapok flakes are crushed, they are oxidized with sodium periodate, and then sequentially reacted with 4-(2-bromoethyl) sodium benzenesulfonate and 4-aminomethylphenylboric acid to obtain modified kapok fibers; functionalized polyacrylonitrile and modified kapok fibers are coaxially spun and then woven to obtain warm skin-friendly fabrics. The warm skin-friendly fabric prepared by the present invention has excellent warmth retention, skin-friendliness, flame retardancy, antibacterial properties, antistatic properties and mechanical properties.

Description

Technical Field

[0001] The invention relates to the field of fabrics, in particular to a warm-keeping skin-friendly fabric and a preparation method thereof. Background Art

[0002] With the development of social industrial level and increasingly severe global climate change, people have put forward higher requirements for the thermal insulation performance of thermal insulation materials. According to the source of fiber, thermal insulation materials can be divided into natural thermal insulation materials and synthetic thermal insulation materials. Kapok fiber is a hollow structure with closed ends, which can store a large amount of static air, so that it has good thermal insulation performance. However, natural thermal insulation materials generally have the characteristics of high moisture regain, fiber materials absorb moisture in the air, causing the human body to feel damp and cold in a cold environment, greatly reducing the thermal insulation performance of fiber materials, thereby limiting its application in the field of thermal insulation clothing. Synthetic fiber materials have made up for the performance defects of natural fibers to a certain extent, and with the maturity and development of fiber material preparation technology, the output has been greatly increased while the price has been greatly reduced. Nowadays, various synthetic fiber materials such as polyester, acrylic fiber, viscose, etc. have gradually replaced natural fiber materials to become the most widely used thermal insulation materials. Acrylic fiber has the advantages of low moisture regain, good thermal insulation, less affected by environmental temperature and humidity, low cost, etc., but at the same time, it also has the disadvantages of easy generation of static electricity and poor comfort. Therefore, the present invention uses a coaxial spinning method to prepare a warm skin-friendly fabric with excellent antistatic performance. Summary of the invention

[0003] The object of the present invention is to provide a warm skin-friendly fabric and a preparation method thereof, so as to solve the problems existing in the prior art.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] A warm skin-friendly fabric is obtained by coaxially spinning functionalized polyacrylonitrile and modified kapok fiber and then weaving them.

[0006] As an optimization, the functionalized polyacrylonitrile is obtained by reacting polyacrylonitrile powder, glycidyl acrylate and allyl dimethyl phosphate, and then reacting with 3-amino-1,2-propylene glycol and dicyandiamide in sequence.

[0007] As an optimization, the polyacrylonitrile powder comes from Hengtai Plastic Raw Materials Business Department in Zhangmutou, Dongguan City.

[0008] As an optimization, the modified kapok fiber is obtained by crushing kapok flakes, oxidizing them with sodium periodate, and then reacting them with sodium 4-(2-bromoethyl)benzenesulfonate and 4-aminomethylphenylboronic acid in sequence.

[0009] As an optimization, the kapok cotton sheet model is MM032, which comes from Shandong Aorong Garment Co., Ltd.

[0010] A method for preparing a warm skin-friendly fabric comprises the following preparation steps:

[0011] (1) Polyacrylonitrile powder, glycidyl acrylate, dimethyl allyl phosphate, benzophenone and methanol were mixed in a mass ratio of 1:(2-4):(2.3-2.5):(0.2-0.4):(10-11), ultrasonicated at 45-55°C for 1-3 hours, filtered, irradiated under a 360-370 nm ultraviolet lamp for 25-35 minutes, extracted in an acetone Soxhlet extractor for 11-13 hours, and washed with deionized water for 3-5 times. , drying at 55-65°C for 15-17h to obtain pre-modified polyacrylonitrile; mixing pre-modified polyacrylonitrile, 3-amino-1,2-propylene glycol and deionized water in a mass ratio of 1:(2-3):(6-8), stirring at 80-90°C and 100-200rpm for 1-3h, naturally cooling to room temperature and filtering, washing with anhydrous ethanol and deionized water for 3-5 times respectively, and drying at 75-85°C for 10-12h to obtain modified polyacrylonitrile;

[0012] (2) dicyandiamide and deionized water are mixed in a mass ratio of 1:(8-10), stirred at 60-70° C. and 100-200 rpm for 20-30 min, a hydrochloric acid solution with a mass fraction of 10-20% is added to adjust the pH to 4-5, modified polyacrylonitrile with a mass of 2-3 times that of dicyandiamide is added, the temperature is raised to 70-80° C. and stirring is continued for 2-4 h, the mixture is naturally cooled to room temperature and then filtered, washed with deionized water for 3-5 times, and dried at 65-75° C. for 8-10 h to obtain functionalized polyacrylonitrile;

[0013] (3) Crush kapok flakes to a particle size of 250-350 nm to obtain kapok fibers; mix the kapok fibers and 1-3 g / L sodium periodate aqueous solution at a mass ratio of 1:(99-101), stir at 35-45° C. and 100-200 rpm for 55-65 min, filter, wash with deionized water for 3-5 times, and dry at 65-75° C. for 6-8 h to obtain oxidized kapok fibers; mix the oxidized kapok fibers, 0.09-0.11 mol / L sodium hydroxide solution and deionized water at a mass ratio of 1:(3-5):(20-30), stir at 20-30° C. and 100-200 rpm for 0.5-1.5 h, add 54-56 times the mass of the oxidized kapok fibers, 4-6 times the mass of the oxidized kapok fibers, and 100-200 rpm of sodium hydroxide to obtain oxidized kapok fibers; -(2-bromoethyl) benzene sulfonate and a sodium hydroxide solution with a mass fraction of 35-45% of 6-8 times the mass of oxidized kapok fiber, heated to 35-45°C, stirred at 150-250r / min for 2-3h, naturally cooled to room temperature and filtered, washed with deionized water for 3-5 times, dried at 60-70°C for 11-13h, to obtain pre-modified kapok fiber; pre-modified kapok fiber, 4-aminomethylphenylboric acid, acetic acid and methanol were mixed in a mass ratio of 1: (1.6-1.8): (0.4-0.6): (80-90), stirred at 70-80°C and 200-300rpm for 12-14h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol for 3-5 times, dried at 55-65°C for 11-13h, to obtain modified kapok fiber;

[0014] (4) Functionalized polyacrylonitrile and N,N-dimethylformamide are mixed in a mass ratio of 1:(6-7), and stirred at 20-30°C and 1400-1600 r / min for 11-12 hours to obtain a core layer spinning solution; modified kapok fiber and N,N-dimethylacetamide are mixed in a mass ratio of 1:(7-8), and stirred at 20-30°C and 700-900 r / min for 1-2 hours to obtain a shell layer spinning solution; the core layer spinning solution and the shell layer spinning solution are electrostatically spun using a coaxial needle at a temperature of 20-30°C, a humidity of 15-25%, a receiving distance of 17-19 cm, a voltage of 15-25 kV, and a propulsion speed of 350-450 μL / min. After completion, the spinning solution is allowed to stand at 80-90°C for 8-10 hours to obtain a warm skin-friendly fiber; the warm skin-friendly fiber is spun and woven by a textile machine to obtain a warm skin-friendly fabric.

[0015] As an optimization, the reaction equation of the pre-modified polyacrylonitrile in step (1) is:

[0016]

[0017] As an optimization, the reaction equation for modifying polyacrylonitrile in step (1) is:

[0018]

[0019] As an optimization, the reaction equation of the functionalized polyacrylonitrile in step (2) is:

[0020]

[0021] As an optimization, the reaction equation of the pre-modified kapok fiber in step (3) is:

[0022]

[0023] As an optimization, the reaction equation of the modified kapok fiber in step (3) is:

[0024]

[0025] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0026] When preparing the warm skin-friendly fabric, the present invention comprises the following steps: reacting polyacrylonitrile powder, glycidyl acrylate and allyl dimethyl phosphate to obtain pre-modified polyacrylonitrile; then reacting the pre-modified polyacrylonitrile with 3-amino-1,2-propylene glycol and dicyandiamide in sequence to obtain functionalized polyacrylonitrile; crushing kapok flakes and oxidizing them with sodium periodate, and then reacting them with sodium 4-(2-bromoethyl)benzenesulfonate and 4-aminomethylphenylboric acid in sequence to obtain modified kapok fibers; and coaxially spinning the functionalized polyacrylonitrile and the modified kapok fibers to obtain the warm skin-friendly fabric.

[0027] Firstly, polyacrylonitrile powder, glycidyl acrylate and allyl dimethyl phosphate are reacted to obtain pre-modified polyacrylonitrile; then the pre-modified polyacrylonitrile is reacted with 3-amino-1,2-propylene glycol and dicyandiamide in sequence to obtain functionalized polyacrylonitrile; allyl dimethyl phosphate is grafted onto polyacrylonitrile using ultraviolet light, and the introduced phosphorus element can be decomposed during combustion to generate phosphate free radicals and phosphate acetals, which react with oxygen to form a protective layer, inhibit the combustion reaction, and improve the flame retardant properties of warm and skin-friendly fabrics; 3-amino-1,2-propylene glycol is grafted through the reaction of epoxy and amino groups, and a vicinal diol structure that easily reacts with boric acid groups to form a borate ester bond is introduced, forming a cross-linked network between kapok fiber and polyacrylonitrile, thereby improving the mechanical properties of warm and skin-friendly fabrics; dicyandiamide is further grafted to form a biguanide structure that destroys cell metabolism and inhibits bacterial growth, thereby improving the antibacterial properties of warm and skin-friendly fabrics.

[0028] Secondly, the kapok flakes are crushed and oxidized with sodium periodate, and then reacted with sodium 4-(2-bromoethyl)benzenesulfonate and 4-aminomethylphenylboric acid in sequence to obtain modified kapok fibers; the functionalized polyacrylonitrile and the modified kapok fibers are coaxially spun and woven to obtain warm and skin-friendly fabrics; 4-(2-bromoethyl)benzenesulfonate is grafted onto the oxidized kapok fibers, which can effectively adsorb and neutralize static charges, improve the antistatic properties of the warm and skin-friendly fabrics, and can also electrostatically bond with the cationic part of biguanide to improve the mechanical properties of the warm and skin-friendly fabrics; 4-aminomethylphenylboric acid is grafted using a Schiff base reaction, which can react with the vicinal diol on the functionalized polyacrylonitrile to form a borate ester bond, further improving the mechanical properties of the warm and skin-friendly fabrics; kapok fibers, a natural thermal insulation material with many tiny air pockets, are used as a shell layer by coaxial spinning and wrapped around the polyacrylonitrile to provide a more comfortable wearing experience and enhance the warmth and skin-friendliness of the fabric. DETAILED DESCRIPTION

[0029] 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.

[0030] Example 1

[0031] A method for preparing a warm skin-friendly fabric, the method comprising the following preparation steps:

[0032] (1) polyacrylonitrile powder, glycidyl acrylate, dimethyl allyl phosphate, benzophenone and methanol were mixed in a mass ratio of 1:2:2.3:0.2:10, and filtered after ultrasonic treatment at 45°C for 3 hours, irradiated under a 360nm ultraviolet lamp for 35 minutes, extracted in an acetone Soxhlet extractor for 11 hours, washed with deionized water for 3 times, and dried at 55°C for 17 hours to obtain pre-modified polyacrylonitrile; pre-modified polyacrylonitrile, 3-amino-1,2-propanediol and deionized water were mixed in a mass ratio of 1:2:6, stirred at 80°C and 100 rpm for 3 hours, naturally cooled to room temperature, filtered, washed with anhydrous ethanol and deionized water for 3 times respectively, and dried at 75°C for 12 hours to obtain modified polyacrylonitrile;

[0033] (2) Dicyandiamide and deionized water were mixed in a mass ratio of 1:8, stirred at 60°C and 100 rpm for 30 min, a 10% hydrochloric acid solution was added to adjust the pH to 4, and modified polyacrylonitrile with a mass fraction of 2 times that of dicyandiamide was added, the temperature was raised to 70°C and stirred for 4 h, and the mixture was naturally cooled to room temperature and filtered, washed with deionized water for 3 times, and dried at 65°C for 10 h to obtain functionalized polyacrylonitrile;

[0034] (3) Crush the kapok flakes to a particle size of 250 nm to obtain kapok fibers; mix the kapok fibers and 1 g / L sodium periodate aqueous solution at a mass ratio of 1:99, stir at 35°C and 100 rpm for 65 min, filter, wash with deionized water three times, and dry at 65°C for 8 h to obtain oxidized kapok fibers; mix the oxidized kapok fibers, 0.09 mol / L sodium hydroxide solution and deionized water at a mass ratio of 1:3:20, stir at 20°C and 100 rpm for 1.5 h, add 54 times the mass of the oxidized kapok fibers, 6 times the mass of the oxidized kapok fibers, and 4- Sodium (2-bromoethyl) benzene sulfonate and a 35% sodium hydroxide solution with a mass fraction of 6 times the mass of oxidized kapok fiber were heated to 35°C and stirred at 150r / min for 3h, naturally cooled to room temperature and filtered, washed with deionized water for 3 times, and dried at 60°C for 13h to obtain pre-modified kapok fiber; pre-modified kapok fiber, 4-aminomethylphenylboric acid, acetic acid and methanol were mixed in a mass ratio of 1:1.6:0.4:80, stirred at 70°C and 200rpm for 14h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol for 3 times, and dried at 55°C for 13h to obtain modified kapok fiber;

[0035] (4) Functionalized polyacrylonitrile and N,N-dimethylformamide were mixed in a mass ratio of 1:6, and stirred at 20°C and 1400 r / min for 12 h to obtain a core layer spinning solution; modified kapok fiber and N,N-dimethylacetamide were mixed in a mass ratio of 1:7, and stirred at 20°C and 700 r / min for 2 h to obtain a shell layer spinning solution; the core layer spinning solution and the shell layer spinning solution were electrospun using a coaxial needle at a temperature of 20°C, a humidity of 15%, a receiving distance of 17 cm, a voltage of 15 kV, and a propulsion speed of 350 μL / min. After completion, the spinning was allowed to stand at 80°C for 10 h to obtain a warm skin-friendly fiber; the warm skin-friendly fiber was spun and woven by a textile machine to obtain a warm skin-friendly fabric.

[0036] Example 2

[0037] A method for preparing a warm skin-friendly fabric, the method comprising the following preparation steps:

[0038] (1) polyacrylonitrile powder, glycidyl acrylate, dimethyl allyl phosphate, benzophenone and methanol were mixed in a mass ratio of 1:3:2.4:0.3:10.5, and filtered after ultrasonic treatment at 50°C for 2 hours, irradiated under a UV lamp with a wavelength of 365 nm for 30 minutes, extracted in an acetone Soxhlet extractor for 12 hours, washed with deionized water for 4 times, and dried at 60°C for 16 hours to obtain pre-modified polyacrylonitrile; pre-modified polyacrylonitrile, 3-amino-1,2-propanediol and deionized water were mixed in a mass ratio of 1:2.5:7, stirred at 85°C and 150 rpm for 2 hours, naturally cooled to room temperature, filtered, washed with anhydrous ethanol and deionized water for 4 times respectively, and dried at 80°C for 11 hours to obtain modified polyacrylonitrile;

[0039] (2) Dicyandiamide and deionized water were mixed in a mass ratio of 1:9, stirred at 65°C and 150 rpm for 25 min, a 15% hydrochloric acid solution was added to adjust the pH to 4.5, and modified polyacrylonitrile with a mass fraction of 2.5 times that of dicyandiamide was added, the temperature was raised to 75°C and stirred for 3 h, and the mixture was naturally cooled to room temperature and filtered, washed with deionized water for 4 times, and dried at 70°C for 9 h to obtain functionalized polyacrylonitrile;

[0040] (3) Crush the kapok flakes to a particle size of 300 nm to obtain kapok fibers; mix the kapok fibers and 2 g / L sodium periodate aqueous solution at a mass ratio of 1:100, stir at 40°C and 150 rpm for 60 min, filter, wash with deionized water 4 times, and dry at 70°C for 7 h to obtain oxidized kapok fibers; mix the oxidized kapok fibers, 0.1 mol / L sodium hydroxide solution and deionized water at a mass ratio of 1:4:25, stir at 25°C and 150 rpm for 1 h, add 55 times the mass of the oxidized kapok fibers, 7 times the mass of the oxidized kapok fibers, and 4-(2 -bromoethyl) benzene sulfonate and 40% sodium hydroxide solution with a mass fraction of 7 times the mass of oxidized kapok fiber, heated to 40°C, stirred at 200r / min for 2.5h, naturally cooled to room temperature and filtered, washed with deionized water 4 times, dried at 65°C for 12h, to obtain pre-modified kapok fiber; pre-modified kapok fiber, 4-aminomethylphenylboric acid, acetic acid and methanol were mixed in a mass ratio of 1:1.7:0.5:85, stirred at 75°C and 250rpm for 13h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol 4 times, dried at 60°C for 12h, to obtain modified kapok fiber;

[0041] (4) Functionalized polyacrylonitrile and N,N-dimethylformamide were mixed at a mass ratio of 1:6.5, and stirred at 25°C and 1500 r / min for 11.5 h to obtain a core layer spinning solution; modified kapok fiber and N,N-dimethylacetamide were mixed at a mass ratio of 1:7.5, and stirred at 25°C and 800 r / min for 1.5 h to obtain a shell layer spinning solution; the core layer spinning solution and the shell layer spinning solution were electrostatically spun using a coaxial needle at a temperature of 25°C, a humidity of 20%, a receiving distance of 18 cm, a voltage of 20 kV, and a propulsion speed of 400 μL / min. After completion, the spinning was allowed to stand at 85°C for 9 h to obtain a warm skin-friendly fiber; the warm skin-friendly fiber was spun and woven by a textile machine to obtain a warm skin-friendly fabric.

[0042] Example 3

[0043] A method for preparing a warm skin-friendly fabric, the method comprising the following preparation steps:

[0044] (1) polyacrylonitrile powder, glycidyl acrylate, dimethyl allyl phosphate, benzophenone and methanol were mixed in a mass ratio of 1:4:2.5:0.4:11, ultrasonicated at 55°C for 1 hour, filtered, irradiated under a UV lamp with a wavelength of 370 nm for 25 minutes, extracted in an acetone Soxhlet extractor for 13 hours, washed with deionized water for 5 times, and dried at 65°C for 15 hours to obtain pre-modified polyacrylonitrile; pre-modified polyacrylonitrile, 3-amino-1,2-propanediol and deionized water were mixed in a mass ratio of 1:3:8, stirred at 90°C and 200 rpm for 1 hour, naturally cooled to room temperature, filtered, washed with anhydrous ethanol and deionized water for 5 times respectively, and dried at 85°C for 10 hours to obtain modified polyacrylonitrile;

[0045] (2) Dicyandiamide and deionized water were mixed in a mass ratio of 1:10, stirred at 70°C and 200 rpm for 20 min, a 20% hydrochloric acid solution was added to adjust the pH to 5, and modified polyacrylonitrile with a mass of 3 times that of dicyandiamide was added, the temperature was raised to 80°C and stirred for 2 h, and the mixture was naturally cooled to room temperature and filtered, washed with deionized water for 5 times, and dried at 75°C for 8 h to obtain functionalized polyacrylonitrile;

[0046] (3) Crush the kapok flakes to a particle size of 350 nm to obtain kapok fibers; mix the kapok fibers and 3 g / L sodium periodate aqueous solution at a mass ratio of 1:101, stir at 45°C and 200 rpm for 55 min, filter, wash with deionized water 5 times, and dry at 75°C for 6 h to obtain oxidized kapok fibers; mix the oxidized kapok fibers, 0.11 mol / L sodium hydroxide solution and deionized water at a mass ratio of 1:5:30, stir at 30°C and 200 rpm for 0.5 h, add 56 times the mass of the oxidized kapok fibers, 8 times the mass of the oxidized kapok fibers, and 4- Sodium (2-bromoethyl) benzene sulfonate and a 45% sodium hydroxide solution with a mass fraction of 8 times the mass of oxidized kapok fiber were heated to 45°C and stirred at 250r / min for 2h, naturally cooled to room temperature and filtered, washed with deionized water 5 times, and dried at 70°C for 11h to obtain pre-modified kapok fiber; pre-modified kapok fiber, 4-aminomethylphenylboric acid, acetic acid and methanol were mixed in a mass ratio of 1:1.8:0.6:90, stirred at 80°C and 300rpm for 12h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol 5 times, and dried at 65°C for 11h to obtain modified kapok fiber;

[0047] (4) Functionalized polyacrylonitrile and N,N-dimethylformamide were mixed in a mass ratio of 1:7, and stirred at 30°C and 1600 r / min for 11 h to obtain a core layer spinning solution; modified kapok fiber and N,N-dimethylacetamide were mixed in a mass ratio of 1:8, and stirred at 30°C and 900 r / min for 1 h to obtain a shell layer spinning solution; the core layer spinning solution and the shell layer spinning solution were electrospun using a coaxial needle at a temperature of 30°C, a humidity of 25%, a receiving distance of 19 cm, a voltage of 25 kV, and a propulsion speed of 450 μL / min. After completion, the spinning was allowed to stand at 90°C for 8 h to obtain a warm skin-friendly fiber; the warm skin-friendly fiber was spun and woven by a textile machine to obtain a warm skin-friendly fabric.

[0048] Comparative Example 1

[0049] A method for preparing a warm skin-friendly fabric, the method comprising the following preparation steps:

[0050] (1) polyacrylonitrile powder, glycidyl acrylate, dimethyl allyl phosphate, benzophenone and methanol were mixed in a mass ratio of 1:3:2.4:0.3:10.5, and filtered after ultrasonic treatment at 50°C for 2 hours, irradiated under a UV lamp with a wavelength of 365 nm for 30 minutes, extracted in an acetone Soxhlet extractor for 12 hours, washed with deionized water for 4 times, and dried at 60°C for 16 hours to obtain pre-modified polyacrylonitrile; pre-modified polyacrylonitrile, 3-amino-1,2-propanediol and deionized water were mixed in a mass ratio of 1:2.5:7, stirred at 85°C and 150 rpm for 2 hours, naturally cooled to room temperature, filtered, washed with anhydrous ethanol and deionized water for 4 times respectively, and dried at 80°C for 11 hours to obtain modified polyacrylonitrile;

[0051] (2) Crush the kapok flakes to a particle size of 300 nm to obtain kapok fibers; mix the kapok fibers and a 2 g / L sodium periodate aqueous solution at a mass ratio of 1:100, stir at 40°C and 150 rpm for 60 min, filter, wash with deionized water 4 times, and dry at 70°C for 7 h to obtain oxidized kapok fibers; mix the oxidized kapok fibers, a 0.1 mol / L sodium hydroxide solution, and deionized water at a mass ratio of 1:4:25, stir at 25°C and 150 rpm for 1 h, add 55 times the mass of the oxidized kapok fibers, 7 times the mass of the oxidized kapok fibers, and 4-(2 -bromoethyl) benzene sulfonate and 40% sodium hydroxide solution with a mass fraction of 7 times the mass of oxidized kapok fiber, heated to 40°C, stirred at 200r / min for 2.5h, naturally cooled to room temperature and filtered, washed with deionized water 4 times, dried at 65°C for 12h, to obtain pre-modified kapok fiber; pre-modified kapok fiber, 4-aminomethylphenylboric acid, acetic acid and methanol were mixed in a mass ratio of 1:1.7:0.5:85, stirred at 75°C and 250rpm for 13h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol 4 times, dried at 60°C for 12h, to obtain modified kapok fiber;

[0052] (3) Modified polyacrylonitrile and N,N-dimethylformamide were mixed at a mass ratio of 1:6.5, and stirred at 25°C and 1500 r / min for 11.5 h to obtain a core layer spinning solution; modified kapok fiber and N,N-dimethylacetamide were mixed at a mass ratio of 1:7.5, and stirred at 25°C and 800 r / min for 1.5 h to obtain a shell layer spinning solution; the core layer spinning solution and the shell layer spinning solution were electrostatically spun using a coaxial needle at a temperature of 25°C, a humidity of 20%, a receiving distance of 18 cm, a voltage of 20 kV, and a propulsion speed of 400 μL / min. After completion, the spinning was allowed to stand at 85°C for 9 h to obtain a warm skin-friendly fiber; the warm skin-friendly fiber was spun and woven by a textile machine to obtain a warm skin-friendly fabric.

[0053] Comparative Example 2

[0054] A method for preparing a warm skin-friendly fabric, the method comprising the following preparation steps:

[0055] (1) polyacrylonitrile powder, glycidyl acrylate, dimethyl allyl phosphate, benzophenone and methanol were mixed in a mass ratio of 1:3:2.4:0.3:10.5, and filtered after ultrasonic treatment at 50°C for 2 hours, irradiated under a 365 nm ultraviolet lamp for 30 minutes, extracted in an acetone Soxhlet extractor for 12 hours, washed with deionized water for 4 times, and dried at 60°C for 16 hours to obtain pre-modified polyacrylonitrile;

[0056] (2) Crush the kapok flakes to a particle size of 300 nm to obtain kapok fibers; mix the kapok fibers and a 2 g / L sodium periodate aqueous solution at a mass ratio of 1:100, stir at 40°C and 150 rpm for 60 min, filter, wash with deionized water 4 times, and dry at 70°C for 7 h to obtain oxidized kapok fibers; mix the oxidized kapok fibers, a 0.1 mol / L sodium hydroxide solution, and deionized water at a mass ratio of 1:4:25, stir at 25°C and 150 rpm for 1 h, add 55 times the mass of the oxidized kapok fibers, 7 times the mass of the oxidized kapok fibers, and 4-(2 -bromoethyl) benzene sulfonate and 40% sodium hydroxide solution with a mass fraction of 7 times the mass of oxidized kapok fiber, heated to 40°C, stirred at 200r / min for 2.5h, naturally cooled to room temperature and filtered, washed with deionized water 4 times, dried at 65°C for 12h, to obtain pre-modified kapok fiber; pre-modified kapok fiber, 4-aminomethylphenylboric acid, acetic acid and methanol were mixed in a mass ratio of 1:1.7:0.5:85, stirred at 75°C and 250rpm for 13h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol 4 times, dried at 60°C for 12h, to obtain modified kapok fiber;

[0057] (3) Pre-modified polyacrylonitrile and N,N-dimethylformamide were mixed in a mass ratio of 1:6.5, and stirred at 25°C and 1500 r / min for 11.5 h to obtain a core layer spinning solution; modified kapok fiber and N,N-dimethylacetamide were mixed in a mass ratio of 1:7.5, and stirred at 25°C and 800 r / min for 1.5 h to obtain a shell layer spinning solution; the core layer spinning solution and the shell layer spinning solution were electrostatically spun using a coaxial needle at a temperature of 25°C, a humidity of 20%, a receiving distance of 18 cm, a voltage of 20 kV and a propulsion speed of 400 μL / min. After completion, the spinning was allowed to stand at 85°C for 9 h to obtain a warm skin-friendly fiber; the warm skin-friendly fiber was spun and woven by a textile machine to obtain a warm skin-friendly fabric.

[0058] Comparative Example 3

[0059] A method for preparing a warm skin-friendly fabric, the method comprising the following preparation steps:

[0060] (1) Crush kapok flakes to a particle size of 300 nm to obtain kapok fibers; mix the kapok fibers and a 2 g / L sodium periodate aqueous solution at a mass ratio of 1:100, stir at 40°C and 150 rpm for 60 min, filter, wash with deionized water for 4 times, and dry at 70°C for 7 h to obtain oxidized kapok fibers; mix the oxidized kapok fibers, a 0.1 mol / L sodium hydroxide solution, and deionized water at a mass ratio of 1:4:25, stir at 25°C and 150 rpm for 1 h, add deionized water 55 times the mass of the oxidized kapok fibers, 4-(2 -bromoethyl) benzene sulfonate and 40% sodium hydroxide solution with a mass fraction of 7 times the mass of oxidized kapok fiber, heated to 40°C, stirred at 200r / min for 2.5h, naturally cooled to room temperature and filtered, washed with deionized water 4 times, dried at 65°C for 12h, to obtain pre-modified kapok fiber; pre-modified kapok fiber, 4-aminomethylphenylboric acid, acetic acid and methanol were mixed in a mass ratio of 1:1.7:0.5:85, stirred at 75°C and 250rpm for 13h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol 4 times, dried at 60°C for 12h, to obtain modified kapok fiber;

[0061] (2) Polyacrylonitrile and N,N-dimethylformamide were mixed in a mass ratio of 1:6.5, and stirred at 25°C and 1500 r / min for 11.5 h to obtain a core layer spinning solution; modified kapok fiber and N,N-dimethylacetamide were mixed in a mass ratio of 1:7.5, and stirred at 25°C and 800 r / min for 1.5 h to obtain a shell layer spinning solution; the core layer spinning solution and the shell layer spinning solution were electrostatically spun using a coaxial needle at a temperature of 25°C, a humidity of 20%, a receiving distance of 18 cm, a voltage of 20 kV, and a propulsion speed of 400 μL / min. After completion, the spinning was allowed to stand at 85°C for 9 h to obtain a warm skin-friendly fiber; the warm skin-friendly fiber was spun and woven by a textile machine to obtain a warm skin-friendly fabric.

[0062] Comparative Example 4

[0063] A method for preparing a warm skin-friendly fabric, the method comprising the following preparation steps:

[0064] (1) polyacrylonitrile powder, glycidyl acrylate, dimethyl allyl phosphate, benzophenone and methanol were mixed in a mass ratio of 1:3:2.4:0.3:10.5, and filtered after ultrasonic treatment at 50°C for 2 hours, irradiated under a UV lamp with a wavelength of 365 nm for 30 minutes, extracted in an acetone Soxhlet extractor for 12 hours, washed with deionized water for 4 times, and dried at 60°C for 16 hours to obtain pre-modified polyacrylonitrile; pre-modified polyacrylonitrile, 3-amino-1,2-propanediol and deionized water were mixed in a mass ratio of 1:2.5:7, stirred at 85°C and 150 rpm for 2 hours, naturally cooled to room temperature, filtered, washed with anhydrous ethanol and deionized water for 4 times respectively, and dried at 80°C for 11 hours to obtain modified polyacrylonitrile;

[0065] (2) Dicyandiamide and deionized water were mixed in a mass ratio of 1:9, stirred at 65°C and 150 rpm for 25 min, a 15% hydrochloric acid solution was added to adjust the pH to 4.5, and modified polyacrylonitrile with a mass fraction of 2.5 times that of dicyandiamide was added, the temperature was raised to 75°C and stirred for 3 h, and the mixture was naturally cooled to room temperature and filtered, washed with deionized water for 4 times, and dried at 70°C for 9 h to obtain functionalized polyacrylonitrile;

[0066] (3) Crush the kapok flakes to a particle size of 300 nm to obtain kapok fibers; mix the kapok fibers and 2 g / L sodium periodate aqueous solution at a mass ratio of 1:100, stir at 40°C and 150 rpm for 60 min, filter, wash with deionized water 4 times, and dry at 70°C for 7 h to obtain oxidized kapok fibers; mix the oxidized kapok fibers, 0.1 mol / L sodium hydroxide solution and deionized water at a mass ratio of 1:4:25, stir at 25°C and 150 rpm for 1 h, add 55 times the mass of oxidized kapok fibers, 7 times the mass of 4-(2-bromoethyl)benzenesulfonate sodium and 7 times the mass of oxidized kapok fibers, add 40% sodium hydroxide solution, heat to 40°C, stir at 200 r / min for 2.5 h, cool naturally to room temperature, filter, wash with deionized water 4 times, and dry at 65°C for 12 h to obtain pre-modified kapok fibers;

[0067] (4) Functionalized polyacrylonitrile and N,N-dimethylformamide were mixed in a mass ratio of 1:6.5, and stirred at 25°C and 1500 r / min for 11.5 h to obtain a core layer spinning solution; pre-modified kapok fiber and N,N-dimethylacetamide were mixed in a mass ratio of 1:7.5, and stirred at 25°C and 800 r / min for 1.5 h to obtain a shell layer spinning solution; the core layer spinning solution and the shell layer spinning solution were electrostatically spun using a coaxial needle at a temperature of 25°C, a humidity of 20%, a receiving distance of 18 cm, a voltage of 20 kV, and a propulsion speed of 400 μL / min. After completion, the spinning was allowed to stand at 85°C for 9 h to obtain a warm skin-friendly fiber; the warm skin-friendly fiber was spun and woven by a textile machine to obtain a warm skin-friendly fabric.

[0068] Comparative Example 5

[0069] A method for preparing a warm skin-friendly fabric, the method comprising the following preparation steps:

[0070] (1) polyacrylonitrile powder, glycidyl acrylate, dimethyl allyl phosphate, benzophenone and methanol were mixed in a mass ratio of 1:3:2.4:0.3:10.5, and filtered after ultrasonic treatment at 50°C for 2 hours, irradiated under a UV lamp with a wavelength of 365 nm for 30 minutes, extracted in an acetone Soxhlet extractor for 12 hours, washed with deionized water for 4 times, and dried at 60°C for 16 hours to obtain pre-modified polyacrylonitrile; pre-modified polyacrylonitrile, 3-amino-1,2-propanediol and deionized water were mixed in a mass ratio of 1:2.5:7, stirred at 85°C and 150 rpm for 2 hours, naturally cooled to room temperature, filtered, washed with anhydrous ethanol and deionized water for 4 times respectively, and dried at 80°C for 11 hours to obtain modified polyacrylonitrile;

[0071] (2) Dicyandiamide and deionized water were mixed in a mass ratio of 1:9, stirred at 65°C and 150 rpm for 25 min, a 15% hydrochloric acid solution was added to adjust the pH to 4.5, and modified polyacrylonitrile with a mass fraction of 2.5 times that of dicyandiamide was added, the temperature was raised to 75°C and stirred for 3 h, and the mixture was naturally cooled to room temperature and filtered, washed with deionized water for 4 times, and dried at 70°C for 9 h to obtain functionalized polyacrylonitrile;

[0072] (3) Crush the kapok flakes to a particle size of 300 nm to obtain kapok fibers; mix the kapok fibers and a 2 g / L sodium periodate aqueous solution at a mass ratio of 1:100, stir at 40°C and 150 rpm for 60 min, filter, wash with deionized water 4 times, and dry at 70°C for 7 h to obtain oxidized kapok fibers; mix the oxidized kapok fibers, 4-aminomethylphenylboric acid, acetic acid, and methanol at a mass ratio of 1:1.7:0.5:85, stir at 75°C and 250 rpm for 13 h, cool naturally to room temperature, filter, wash with anhydrous ethanol 4 times, and dry at 60°C for 12 h to obtain modified kapok fibers;

[0073] (4) Functionalized polyacrylonitrile and N,N-dimethylformamide were mixed at a mass ratio of 1:6.5, and stirred at 25°C and 1500 r / min for 11.5 h to obtain a core layer spinning solution; modified kapok fiber and N,N-dimethylacetamide were mixed at a mass ratio of 1:7.5, and stirred at 25°C and 800 r / min for 1.5 h to obtain a shell layer spinning solution; the core layer spinning solution and the shell layer spinning solution were electrostatically spun using a coaxial needle at a temperature of 25°C, a humidity of 20%, a receiving distance of 18 cm, a voltage of 20 kV, and a propulsion speed of 400 μL / min. After completion, the spinning was allowed to stand at 85°C for 9 h to obtain a warm skin-friendly fiber; the warm skin-friendly fiber was spun and woven by a textile machine to obtain a warm skin-friendly fabric.

[0074] Test Example 1

[0075] 1. Warmth

[0076] Test method: Take samples of 35 cm × 35 cm in size from the warm and skin-friendly fabrics obtained in each embodiment and the comparative example according to GB / T35762, and use a YG606G textile thermal resistance tester to measure the thermal conductivity at 35°C.

[0077] 2. Skin-friendly

[0078] Test method: Take samples of 25 cm×3 cm in size from the warm and skin-friendly fabrics obtained in each embodiment and the comparative example, immerse them at the same height in deionized water using a vertical hanging tester, and measure the water rise height after 30 minutes.

[0079] Table 1 below shows the analysis results of the warmth retention and skin-friendliness of the warm skin-friendly fabrics of Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0080] Table 1

[0081] Thermal conductivity mW / mK Wicking height mm Example 1 27.6 231 Example 2 27.4 234 Example 3 28.2 229 Comparative Example 1 28.6 224 Comparative Example 2 27.9 226 Comparative Example 3 28.8 228 Comparative Example 4 28.4 219 Comparative Example 5 27.7 221

[0082] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 1, it can be found that the warm-keeping skin-friendly fabric prepared by the present invention has good warmth retention and skin-friendliness.

[0083] By comparison, the thermal conductivity and wicking height of Examples 1, 2, and 3 compared with Comparative Examples 1 to 5 illustrate that kapok fiber, a natural thermal insulation material with many tiny air pockets, is used as a shell layer through coaxial spinning and wrapped around polyacrylonitrile to provide a more comfortable wearing experience and enhance the warmth retention and skin-friendliness of the fabric.

[0084] Test Example 2

[0085] 1. Flame retardant properties

[0086] Test method: The thermal insulation and skin-friendly fabrics obtained in each embodiment and the comparative example were tested for limiting oxygen index according to GB / T5454.

[0087] 2. Antibacterial properties

[0088] Test method: Take 5mm×5mm samples of the warm skin-friendly fabrics obtained in each embodiment and the comparative example according to GB / T20944, put them into 250ml conical flasks (without adding sample as blank control), add 75ml buffer solution and 5ml Escherichia coli inoculum into each flask, oscillate in a constant temperature oscillator for 18h, test the live bacteria concentration respectively, and calculate the inhibition rate = live bacteria concentration of control sample - live bacteria concentration of sample / live bacteria concentration of control sample * 100%.

[0089] 3. Antistatic

[0090] Test method: Take samples of 5 cm×5 cm in size from the warm and skin-friendly fabrics obtained in each embodiment and the comparative example according to GB / T12303, and test the resistance magnitude using a NF453 surface resistance tester at a voltage of 100 V.

[0091] 4. Mechanical properties

[0092] Test method: The warm-keeping skin-friendly fiber obtained in each example and the comparative example were tested for tensile strength according to GB / T14337.

[0093] Table 2 below shows the analysis results of the flame retardant properties, antibacterial properties, antistatic properties and mechanical properties of the warm skin-friendly fabrics of Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0094] Table 2

[0095]

[0096]

[0097] 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 warm skin-friendly fabric prepared by the present invention has good flame retardant properties, antibacterial properties, antistatic properties and mechanical properties.

[0098] By comparison, the antibacterial rate and tensile strength of Examples 1, 2, and 3 are higher than those of Comparative Example 1, which shows that dicyandiamide is grafted onto polyacrylonitrile to form a biguanide structure that destroys cell metabolism and inhibits bacterial growth, thereby improving the antibacterial properties of the warm and skin-friendly fabric; at the same time, it can also electrostatically combine with the anionic part on the kapok fiber to improve the mechanical properties of the warm and skin-friendly fabric.

[0099] By comparison, the antibacterial rate and tensile strength of Examples 1, 2, and 3 are higher than those of Comparative Example 2, which shows that 3-amino-1,2-propylene glycol is grafted onto polyacrylonitrile through the reaction of epoxy groups and amino groups, and a vicinal diol structure that easily reacts with boric acid groups to form a borate ester bond is introduced, forming a cross-linked network between kapok fibers and polyacrylonitrile, thereby improving the mechanical properties of the warm and skin-friendly fabric.

[0100] By comparison, Examples 1, 2, and 3 have higher limiting oxygen index, antibacterial rate, and tensile strength than Comparative Example 3, indicating that by grafting allyl dimethyl phosphate on polyacrylonitrile using ultraviolet light, the introduced phosphorus element can decompose during combustion to generate phosphate free radicals and phosphate acetal, which react with oxygen to form a protective layer, inhibit the combustion reaction, and improve the flame retardant properties of the warm and skin-friendly fabric.

[0101] By comparison, the tensile strength of Examples 1, 2, and 3 is higher than that of Comparative Example 4, which indicates that the grafting of 4-aminomethylphenylboronic acid by Schiff base reaction can react with the vicinal diol on the functionalized polyacrylonitrile to form a borate ester bond, thereby improving the mechanical properties of the warm and skin-friendly fabric.

[0102] By comparison, the resistance of Examples 1, 2, and 3 is lower than that of Comparative Example 5 and the tensile strength is higher, which shows that grafting sodium 4-(2-bromoethyl)benzenesulfonate on the oxidized kapok fiber can effectively adsorb and neutralize static charge, thereby improving the antistatic property of the warm and skin-friendly fabric; at the same time, it can also electrostatically combine with the cationic part of the biguanide to improve the mechanical properties of the warm and skin-friendly fabric.

[0103] 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 warm skin-friendly fabric, characterized in that: The warm skin-friendly fabric is obtained by coaxially spinning functionalized polyacrylonitrile and modified kapok fiber and then weaving; The core spinning solution of the coaxial spinning is obtained by mixing functionalized polyacrylonitrile and N,N-dimethylformamide in a mass ratio of 1:(6-7), and stirring at 20-30° C. and 1400-1600 r / min for 11-12 hours; the shell spinning solution is obtained by mixing modified kapok fiber and N,N-dimethylacetamide in a mass ratio of 1:(7-8), and stirring at 20-30° C. and 700-900 r / min for 1-2 hours; The functionalized polyacrylonitrile is obtained by reacting polyacrylonitrile powder, glycidyl acrylate and allyl dimethyl phosphate, and then reacting with 3-amino-1,2-propylene glycol and dicyandiamide in sequence; The modified kapok fiber is obtained by crushing kapok flakes, oxidizing them with sodium periodate, and then reacting them with sodium 4-(2-bromoethyl)benzenesulfonate and 4-aminomethylphenylboronic acid in sequence.

2. A method for preparing a warm skin-friendly fabric, characterized in that: The method comprises the following preparation steps: (1) Mix polyacrylonitrile powder, glycidyl acrylate, dimethyl allyl phosphate, benzophenone and methanol in a mass ratio of 1:(2-4):(2.3-2.5):(0.2-0.4):(10-11), ultrasonicate at 45-55℃ for 1-3h, filter, irradiate under ultraviolet light at a wavelength of 360-370nm for 25-35min, extract in an acetone Soxhlet extractor for 11-13h, and wash with deionized water 3-5 times. , drying at 55-65°C for 15-17h to obtain pre-modified polyacrylonitrile; mixing pre-modified polyacrylonitrile, 3-amino-1,2-propylene glycol and deionized water in a mass ratio of 1:(2-3):(6-8), stirring at 80-90°C and 100-200rpm for 1-3h, naturally cooling to room temperature and filtering, washing with anhydrous ethanol and deionized water for 3-5 times respectively, and drying at 75-85°C for 10-12h to obtain modified polyacrylonitrile; (2) Dicyandiamide and deionized water are mixed in a mass ratio of 1:(8-10), stirred at 60-70°C and 100-200 rpm for 20-30 min, a hydrochloric acid solution with a mass fraction of 10-20% is added to adjust the pH to 4-5, and modified polyacrylonitrile with a mass of 2-3 times that of dicyandiamide is added, the temperature is raised to 70-80°C and stirring is continued for 2-4 h, the mixture is naturally cooled to room temperature and filtered, washed with deionized water for 3-5 times, and dried at 65-75°C for 8-10 h to obtain functionalized polyacrylonitrile; (3) Crush the kapok flakes to a particle size of 250-350 nm to obtain kapok fibers; mix the kapok fibers and 1-3 g / L sodium periodate aqueous solution at a mass ratio of 1:(99-101), stir at 35-45 °C and 100-200 rpm for 55-65 min, filter, wash with deionized water for 3-5 times, and dry at 65-75 °C for 6-8 h to obtain oxidized kapok fibers; mix the oxidized kapok fibers, 0.09-0.11 mol / L sodium hydroxide solution and deionized water at a mass ratio of 1:(3-5):(20-30), stir at 20-30 °C and 100-200 rpm for 0.5-1.5 h, add 54-56 times the mass of the oxidized kapok fibers, 4-6 times the mass of the oxidized kapok fibers, and 100-200 rpm of sodium hydroxide to obtain oxidized kapok fibers; -(2-bromoethyl) benzene sulfonate sodium and 6-8 times the mass of oxidized kapok fiber with a mass fraction of 35-45% sodium hydroxide solution, heated to 35-45°C, stirred at 150-250r / min for 2-3h, naturally cooled to room temperature and filtered, washed with deionized water for 3-5 times, dried at 60-70°C for 11-13h, to obtain pre-modified kapok fiber; pre-modified kapok fiber, 4-aminomethylphenylboric acid, acetic acid and methanol were mixed in a mass ratio of 1: (1.6-1.8): (0.4-0.6): (80-90), stirred at 70-80°C and 200-300rpm for 12-14h, naturally cooled to room temperature and filtered, washed with anhydrous ethanol for 3-5 times, dried at 55-65°C for 11-13h, to obtain modified kapok fiber; (4) Functionalized polyacrylonitrile and N,N-dimethylformamide were mixed in a mass ratio of 1:(6-7), and stirred at 20-30°C and 1400-1600 r / min for 11-12 h to obtain a core layer spinning solution; modified kapok fiber and N,N-dimethylacetamide were mixed in a mass ratio of 1:(7-8), and stirred at 20-30°C and 700-900 r / min for 1-2 h to obtain a shell layer spinning solution; the core layer spinning solution and the shell layer spinning solution were electrospun using a coaxial needle at a temperature of 20-30°C, a humidity of 15-25%, a receiving distance of 17-19 cm, a voltage of 15-25 kV, and a propulsion speed of 350-450 μL / min. After completion, the spinning solution was allowed to stand at 80-90°C for 8-10 h to obtain a warm skin-friendly fiber; the warm skin-friendly fiber was spun and woven by a textile machine to obtain a warm skin-friendly fabric.

3. The method for preparing a warm skin-friendly fabric according to claim 2, characterized in that: The reaction equation of the pre-modified polyacrylonitrile in step (1) is: 。 4. The method for preparing a warm skin-friendly fabric according to claim 2, characterized in that: The reaction equation for modifying polyacrylonitrile in step (1) is: 。 5. The method for preparing a warm skin-friendly fabric according to claim 2, characterized in that: The reaction equation of the functionalized polyacrylonitrile in step (2) is: 。 6. The method for preparing a warm skin-friendly fabric according to claim 2, characterized in that: The reaction equation of the pre-modified kapok fiber in step (3) is: 。 7. The method for preparing a warm skin-friendly fabric according to claim 2, characterized in that: The reaction equation of the modified kapok fiber in step (3) is: 。

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