A cool, washable bio-based nylon 56 fabric and its preparation method

Abstract

The present invention relates to the field of textile technology, and discloses a cool feeling and washable bio-based nylon 56 fabric and a preparation method thereof. The preparation method of the cool feeling and washable bio-based nylon 56 fabric comprises the following steps: modified nano-alumina is loaded on modified aluminum nitride micro-sheets to obtain a composite cool material; nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polypentamethyleneguanidine hydrochloride, and a composite cool material are co-extruded, melt-spun, and then woven into a bio-based nylon 56 fabric; composite modified boron nitride and ethanol are mixed to obtain a finishing liquid; the finishing liquid is sprayed on one side of the bio-based nylon 56 fabric and dried to obtain a cool feeling and washable bio-based nylon 56 fabric. The cool feeling and washable bio-based nylon 56 fabric of the present invention has excellent cool feeling, antibacterial performance, washability, moisture absorption performance and unidirectional perspiration performance.

Description

Technical Field

[0001] The invention relates to the technical field of textiles, in particular to a cool, washable bio-based nylon 56 fabric and a preparation method thereof. Background Art

[0002] Nylon materials are widely used in clothing, automobiles, fishing gear, building materials and other fields, and are closely related to people's daily lives. Nylon 6 is a common nylon material, but the cool feeling of conventional nylon 6 fabrics or textiles is not sustained and has poor moisture absorption. In addition, the raw materials of nylon 6 are all derived from petroleum. With the gradual depletion of petroleum resources and the enhancement of global environmental awareness, the environmentally friendly bio-based PA56 (nylon 56) prepared by bioconversion of 1,5-pentanediamine (PDA) has attracted widespread attention.

[0003] PA56 fabrics offer excellent dyeing, softness, and antistatic properties. Furthermore, their excellent moisture absorption provides tremendous opportunities for the textile industry. However, PA56 fabrics' cooling and antibacterial properties need improvement, especially in the hot summer months, which hinders their ability to meet people's demands for comfortable, healthy, and safe clothing. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a method for preparing a cool and washable bio-based nylon 56 fabric, comprising the following steps:

[0005] Step 1: reacting 1,5-pentanediamine with guanidine hydrochloride to obtain polypentamethyleneguanidine hydrochloride;

[0006] Step 2: Alumina nanoparticles are modified with polydopamine to obtain modified nano-alumina; aluminum nitride microsheets are modified with γ-glycidyloxypropyltrimethoxysilane to obtain modified aluminum nitride microsheets; the modified nano-alumina is loaded on the modified aluminum nitride microsheets to obtain a composite cooling material;

[0007] Step 3: nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polypentamethyleneguanidine hydrochloride, and the composite cooling material are blended and extruded, melt-spun, and then woven into a bio-based nylon 56 fabric;

[0008] Step 4: Mixing the composite modified boron nitride and ethanol to obtain a finishing solution; spraying the finishing solution on one side of the bio-based nylon 56 fabric, and drying to obtain a cool and washable bio-based nylon 56 fabric;

[0009] The preparation method of the composite modified boron nitride comprises the following steps:

[0010] Step S1, hexagonal boron nitride is modified with a silane coupling agent KH550 to obtain surface-modified boron nitride;

[0011] Step S2, treating the surface-modified boron nitride with an antibacterial modification liquid containing glycidyl trimethylammonium chloride to obtain antibacterial modified boron nitride;

[0012] Step S3: treating the antibacterial modified boron nitride with a fluorine-containing modification liquid containing pentadecafluorooctanoyl chloride to obtain composite modified boron nitride.

[0013] Preferably, in the step 1, during the preparation of the polypentamethyleneguanidine hydrochloride: 1,5-pentanediamine and guanidine hydrochloride are mixed in equal molar ratios, and the reaction conditions are: first reacting at 115-125° C. for 1.5-2.5 hours, then heating to 190-210° C. for 5.5-7.5 hours, and the reaction by-product ammonia is absorbed with a 37% mass fraction hydrochloric acid aqueous solution;

[0014] Preferably, in step 2, the preparation method of the modified nano-alumina comprises: mixing dopamine hydrochloride, Tris-HCl buffer with a pH of 8.5, and ethanol in a ratio of (0.18-0.2) g: (150-180) mL: (50-60) mL to obtain a modification solution; adding alumina nanoparticles to the modification solution for soaking, stirring at 24-26° C. for 20-28 hours, filtering, washing, and drying to obtain modified nano-alumina; wherein the ratio of the alumina nanoparticles to the modification solution is (10-15) g: (100-120) mL;

[0015] In the above process: under alkaline conditions, dopamine polymerizes on the surface of alumina nanoparticles to generate polydopamine, thereby obtaining modified nano-alumina.

[0016] Preferably, in step 2, the preparation method of the modified aluminum nitride microsheets is as follows: aluminum nitride microsheet powder and ethanol are mixed in a mass ratio of (6-10): (80-100), and ultrasonic treatment is performed for 20-40 minutes to obtain a mixed solution A; γ-glycidyloxypropyltrimethoxysilane and ethanol are mixed in a mass ratio of (0.5-0.8): (60-80), and stirred at 65-75° C. for 4-6 hours to obtain a mixed solution B; under stirring conditions, the mixed solution A is added to the mixed solution B, the temperature is maintained at 65-75° C., and stirred for 1.5-2.5 hours, filtered, washed, and dried to obtain modified aluminum nitride microsheets;

[0017] In the above process: γ-glycidyloxypropyltrimethoxysilane is used to modify the aluminum nitride microchips and epoxy groups are introduced on their surfaces.

[0018] Preferably, in step 2, the preparation method of the composite cooling material is as follows: modified nano-alumina, modified aluminum nitride microsheets, and toluene are mixed in a mass ratio of (2-3): (10-16): (150-200), ultrasonicated at 200-300W for 10-20min, then heated to 110-130°C in a nitrogen atmosphere, reacted for 3.5-4.5h, and after the reaction, centrifuged, washed, and dried to obtain the composite cooling material;

[0019] In the above process, the amino groups on the surface of the polydopamine on the surface of the modified nano-alumina react with the epoxy groups on the surface of the modified aluminum nitride micro-sheets, and the modified nano-alumina is loaded on the modified aluminum nitride micro-sheets.

[0020] Preferably, in the step three, the mass ratio of the nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polypentamethyleneguanidine hydrochloride, and the composite cooling material is 98:1:(1-1.5):(0.4-1).

[0021] Preferably, in step 3, the blending extrusion conditions are: temperature of 250-270°C, rotation speed of 40-60 rpm; melt spinning temperature of 280-290°C; weight of bio-based nylon 56 fabric of 120-150 g / m 2 .

[0022] Preferably, in step 4, the mass ratio of the composite modified boron nitride and ethanol is (0.2-0.4):1; the spraying amount of the finishing liquid is 140-160g / m 2 .

[0023] Furthermore, in the step 4, the preparation method of the composite modified boron nitride comprises the following steps:

[0024] Step S1, dispersing hexagonal boron nitride in an 80% by mass ethanol aqueous solution, then adding a silane coupling agent KH550 thereto, stirring and reacting at 55-65° C. for 2-3 hours, filtering, washing, and drying to obtain surface-modified boron nitride; wherein the amount ratio of hexagonal boron nitride, ethanol aqueous solution, and silane coupling agent KH550 is (10-15) g: (100-120) mL: (1-3) g;

[0025] In the above process: hexagonal boron nitride is modified by silane coupling agent KH550, and a large number of amino groups are introduced on its surface;

[0026] Step S2, mixing equal volumes of deionized water and ethanol to form an ethanol aqueous solution; adding glycidyltrimethylammonium chloride to the ethanol aqueous solution to obtain an antibacterial modification liquid with a mass fraction of 5%; adding surface-modified boron nitride to the antibacterial modification liquid, adjusting the pH of the mixed system to 8.5 with sodium carbonate-sodium bicarbonate buffer, stirring and reacting at 38-42° C. for 7-9 hours, and after the reaction is completed, filtering, washing, and drying to obtain antibacterial modified boron nitride; wherein the mass ratio of surface-modified boron nitride to antibacterial modification liquid is (8-10):(100-150);

[0027] In the above process: the epoxy group of glycidyl trimethylammonium chloride reacts with some amino groups on the surface-modified boron nitride, introducing a quaternary ammonium salt structure with antibacterial effect on the boron nitride;

[0028] Step S3, 15-fluorooctanoyl chloride and tetrahydrofuran are mixed in a mass ratio of (0.8-1.6): (15-20), and stirred in a nitrogen atmosphere for 1.5-2.5 hours to obtain a fluorine-containing modified liquid; the antibacterial modified boron nitride is dispersed in ethanol, and then mixed with the above-mentioned fluorine-containing modified liquid, stirred for reaction for 12-14 hours, and then a sodium bicarbonate aqueous solution with a mass fraction of 7.5% is added, the precipitate is collected by suction filtration, and dried to obtain a composite modified boron nitride; wherein the mass ratio of the antibacterial modified boron nitride, ethanol, fluorine-containing modified liquid, and sodium bicarbonate aqueous solution is (8-10): (80-100): (15.8-21.6): (2.1-4.2);

[0029] In the above process, the acyl chloride group in pentadecafluorooctanoyl chloride reacts with part of the amino groups on the surface of the antibacterial modified boron nitride, and a hydrophobic fluorine-containing chain is introduced on the surface of the boron nitride.

[0030] The cool and washable bio-based nylon 56 fabric is prepared by adopting the preparation method of the cool and washable bio-based nylon 56 fabric.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] 1. The present invention replaces the traditional petroleum-based nylon fabric with bio-based nylon 56 fabric.

[0033] Reduce the use of fossil raw materials and be more environmentally friendly.

[0034] 2. The present invention comprises the following steps: nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polypentamethyleneguanidine hydrochloride, and a composite cooling material are co-extruded, melt-spun, and then woven into a bio-based nylon 56 fabric; polypentamethyleneguanidine hydrochloride serves as a bio-based antibacterial agent, imparting excellent antibacterial properties to the bio-based nylon 56 fabric; the presence of epoxy groups in the ethylene-methyl acrylate-glycidyl methacrylate terpolymer enables polypentamethyleneguanidine hydrochloride and the composite cooling material to be grafted onto nylon 56 in the form of chemical bonds, thereby improving the compatibility of polypentamethyleneguanidine hydrochloride, the composite cooling material, and nylon 56, thereby improving the mechanical properties of the bio-based nylon 56 fabric and, more importantly, enabling the bio-based nylon 56 fabric to maintain a long-lasting cooling sensation and antibacterial properties;

[0035] Furthermore, the composite cooling material of the present invention is prepared by loading modified nano-alumina on modified aluminum nitride microsheets. Both nano-alumina and aluminum nitride are inorganic materials with excellent thermal conductivity. Loading the modified nano-alumina on the modified aluminum nitride microsheets helps to form more thermal conductive networks, so that the thermal conductivity of the composite cooling material is better. In addition, nano-alumina also has good sunlight reflection ability, which can reduce the absorption of sunlight. Starting from the two aspects of thermal conductivity and sunlight reflection, the cooling feeling of bio-based nylon 56 fabric is improved; in addition, nano-alumina also has good hydrophilic properties. After modification with polydopamine, the hydrophilicity is further improved, thereby improving the moisture absorption and air permeability of bio-based nylon 56 fabric. The introduction of amino groups in polydopamine provides reactive groups for the grafting of the composite cooling material with nylon 56 and ethylene-methyl acrylate-glycidyl methacrylate terpolymer, so that the composite cooling material is more evenly dispersed, thereby exerting better efficacy.

[0036] 3. The present invention sequentially modifies hexagonal boron nitride with a silane coupling agent KH550, glycidyltrimethylammonium chloride, and pentafluorooctanoyl chloride to obtain a composite modified boron nitride. Hexagonal boron nitride is an inorganic material with excellent thermal conductivity. Glycidyltrimethylammonium chloride and a fluorine-containing hydrophobic chain with antibacterial properties are grafted onto the hexagonal boron nitride. The finishing liquid containing the composite modified boron nitride is then sprayed onto one side of a bio-based nylon 56 fabric, thereby improving the antibacterial properties and cool feel of the bio-based nylon 56 fabric and forming a significant wetting gradient on both sides of the bio-based nylon 56 fabric. When worn, the hydrophobic side contacts the skin to achieve unidirectional rapid evaporation of sweat, keep the skin cool, reduce skin stickiness, and thus improve thermal and wet comfort when worn. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a process flow chart of the preparation method of the cool and washable bio-based nylon 56 fabric of the present invention;

[0038] Figure 2This is a comparison chart of the antibacterial performance test of the cool and washable bio-based nylon 56 fabrics prepared in Examples 2-4 of the present invention and Comparative Examples 2-5 before and after washing;

[0039] Figure 3 This is a comparison chart of moisture regain tests of cool, washable bio-based nylon 56 fabrics prepared in Examples 2-4 of the present invention and Comparative Examples 2-5. DETAILED DESCRIPTION

[0040] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all 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.

[0041] Example 1: This example discloses a method for preparing a composite modified boron nitride, comprising the following steps:

[0042] Step S1, dispersing 12.5 g of hexagonal boron nitride in 110 mL of 80% by mass ethanol aqueous solution, then adding 2 g of silane coupling agent KH550 thereto, stirring and reacting at 60° C. for 2.5 h, filtering, washing, and drying to obtain surface-modified boron nitride;

[0043] Step S2, mixing equal volumes of deionized water and ethanol to form an ethanol aqueous solution; adding glycidyltrimethylammonium chloride to the above ethanol aqueous solution to obtain an antibacterial modification liquid with a mass fraction of 5%; adding 9 g of surface-modified boron nitride to the above 125 g of the antibacterial modification liquid, adjusting the pH of the mixed system to 8.5 with sodium carbonate-sodium bicarbonate buffer, stirring and reacting at 40° C. for 8 hours, and after the reaction is completed, filtering, washing, and drying to obtain antibacterial modified boron nitride;

[0044] Step S3, adding 1.2 g of pentadecafluorooctanoyl chloride to 17.5 g of tetrahydrofuran, stirring for 2 h in a nitrogen atmosphere to obtain a fluorine-containing modified liquid; dispersing 9 g of antibacterial modified boron nitride in 90 g of ethanol, then mixing with the above-mentioned fluorine-containing modified liquid, stirring and reacting for 13 h, then adding 3.3 g of a 7.5% mass fraction of sodium bicarbonate aqueous solution, collecting the precipitate by filtration, and drying to obtain a composite modified boron nitride.

[0045] Example 2: This example discloses a method for preparing a cool, washable bio-based nylon 56 fabric, comprising the following steps:

[0046] Step 1: 1,5-pentanediamine and guanidine hydrochloride are mixed in equal molar ratios, reacted at 115°C for 2.5 hours, then heated to 190°C for 7.5 hours, and the by-product ammonia is absorbed with a 37% hydrochloric acid aqueous solution. After the reaction, the product is vacuum dried at 75°C for 50 hours to obtain polypentamethyleneguanidine hydrochloride;

[0047] Step 2: 0.18 g of dopamine hydrochloride, 150 mL of Tris-HCl buffer (pH 8.5), and 50 mL of ethanol were mixed to obtain a modified solution; 10 g of alumina nanoparticles were added to 100 mL of the modified solution and soaked, stirred at 24° C. for 28 h, filtered with cellulose filter paper, washed three times with deionized water, and dried under vacuum at 55° C. to obtain modified nano-alumina;

[0048] 6 g of aluminum nitride microplatelet powder was added to 80 g of ethanol and ultrasonically treated for 20 minutes to obtain a mixed solution A; 0.5 g of γ-glycidyloxypropyltrimethoxysilane was added to 60 g of ethanol, and the mixture was stirred at 65° C. for 6 hours to obtain a mixed solution B; the mixed solution A was added to the mixed solution B under stirring, and the temperature was maintained at 65° C. and stirred for 2.5 hours, filtered, washed, and dried to obtain modified aluminum nitride microplatelets;

[0049] 3 g of modified nano-alumina and 16 g of modified aluminum nitride microsheets were added to 150 g of toluene, ultrasonicated at 200 W for 20 min, then heated to 110° C. in a nitrogen atmosphere and reacted for 4.5 h. After the reaction, the mixture was centrifuged, washed, and dried to obtain a composite cooling material.

[0050] Step 3, drying nylon 56 in a vacuum drying oven at 100 ° C for 7 hours, and vacuum drying ethylene-methyl acrylate-glycidyl methacrylate terpolymer at 45 ° C for 28 hours, and then mixing nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polypentamethyleneguanidine hydrochloride, and composite cooling material in a mass ratio of 98:1:1:0.4, and blending and extruding them at a temperature of 250 ° C and a speed of 40 rpm using a twin-screw extruder and pelletizing to obtain mixed slices;

[0051] The mixed chips were vacuum dried at 100°C for 10 hours and then melt-spun at 280°C to obtain modified bio-based nylon 56 filaments; the modified bio-based nylon 56 filaments were woven into a 120g / m 2 Bio-based nylon 56 fabric;

[0052] Step 4: Mix the composite modified boron nitride and ethanol in a mass ratio of 0.2:1, and ultrasonicate for 1 hour to obtain a finishing solution; spray the finishing solution on one side of the bio-based nylon 56 fabric at a spraying amount of 150g / m 2, dry to get a cool, washable bio-based nylon 56 fabric.

[0053] Example 3: This example discloses a method for preparing a cool, washable bio-based nylon 56 fabric, comprising the following steps:

[0054] Step 1: 1,5-pentanediamine and guanidine hydrochloride are mixed in equal molar ratios, reacted at 125°C for 1.5 hours, then heated to 210°C for 5.5 hours, and the by-product ammonia is absorbed with a 37% hydrochloric acid aqueous solution. After the reaction, the product is vacuum dried at 80°C for 45 hours to obtain polypentamethyleneguanidine hydrochloride;

[0055] Step 2: 0.2 g of dopamine hydrochloride, 180 mL of Tris-HCl buffer with a pH of 8.5, and 60 mL of ethanol were mixed to obtain a modified solution; 15 g of alumina nanoparticles were added to 120 mL of the modified solution and soaked, stirred at 26°C for 20 h, filtered with cellulose filter paper, washed with deionized water 5 times, and vacuum dried at 65°C to obtain modified nano-alumina;

[0056] 10 g of aluminum nitride microplatelet powder was added to 100 g of ethanol and ultrasonically treated for 40 minutes to obtain a mixed solution A; 0.8 g of γ-glycidyloxypropyltrimethoxysilane was added to 80 g of ethanol, and the mixture was stirred at 75° C. for 6 hours to obtain a mixed solution B; the mixed solution A was added to the mixed solution B under stirring, and the temperature was maintained at 75° C. and stirred for 2.5 hours, and then filtered, washed, and dried to obtain modified aluminum nitride microplatelets;

[0057] 3 g of modified nano-alumina and 16 g of modified aluminum nitride microsheets were added to 200 g of toluene, ultrasonicated at 300 W for 10 min, and then heated to 130° C. in a nitrogen atmosphere for 3.5 h. After the reaction, the mixture was centrifuged, washed, and dried to obtain a composite cooling material.

[0058] Step 3, drying nylon 56 in a vacuum drying oven at 110°C for 5 hours, and vacuum drying ethylene-methyl acrylate-glycidyl methacrylate terpolymer at 55°C for 20 hours, then mixing nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polypentamethyleneguanidine hydrochloride, and the composite cooling material in a mass ratio of 98:1:1.5:1, and extruding and pelletizing them at a temperature of 270°C and a speed of 60 rpm using a twin-screw extruder to obtain mixed slices;

[0059] The mixed chips were vacuum dried at 105°C for 8 hours and then melt-spun at 290°C to obtain modified bio-based nylon 56 filaments; the modified bio-based nylon 56 filaments were woven into a 150g / m 2 Bio-based nylon 56 fabric;

[0060] Step 4: Mix the composite modified boron nitride and ethanol in a mass ratio of 0.4:1, and ultrasonicate for 2 hours to obtain a finishing solution; spray the finishing solution on one side of the bio-based nylon 56 fabric at a spraying amount of 150g / m 2 , dry to get a cool, washable bio-based nylon 56 fabric.

[0061] Example 4: This example discloses a method for preparing a cool, washable bio-based nylon 56 fabric, comprising the following steps:

[0062] Step 1: 1,5-pentanediamine and guanidine hydrochloride are mixed in equal molar ratios, reacted at 120°C for 2 hours, then heated to 200°C for 6.5 hours, and the by-product ammonia is absorbed with a 37% hydrochloric acid aqueous solution. After the reaction, the product is vacuum dried at 78°C for 48 hours to obtain polypentamethyleneguanidine hydrochloride;

[0063] Step 2: 0.19 g of dopamine hydrochloride, 175 mL of Tris-HCl buffer with a pH of 8.5, and 55 mL of ethanol were mixed to obtain a modified solution; 12.5 g of alumina nanoparticles were added to 110 mL of the modified solution and soaked, stirred at 25°C for 24 h, filtered with cellulose filter paper, washed four times with deionized water, and dried in vacuo at 60°C to obtain modified nano-alumina;

[0064] 8 g of aluminum nitride microplatelet powder was added to 90 g of ethanol and ultrasonically treated for 30 minutes to obtain a mixed solution A; 0.7 g of γ-glycidyloxypropyltrimethoxysilane was added to 70 g of ethanol, and the mixture was stirred at 70° C. for 5 hours to obtain a mixed solution B; while stirring, the mixed solution A was added to the mixed solution B, the temperature was maintained at 70° C. and stirred for 2 hours, and the modified aluminum nitride microplatelets were filtered, washed, and dried to obtain modified aluminum nitride microplatelets;

[0065] 2.5 g of modified nano-alumina and 13 g of modified aluminum nitride microsheets were added to 175 g of toluene, and ultrasonicated at 250 W for 15 min. Then, the mixture was heated to 120° C. in a nitrogen atmosphere and reacted for 4 h. After the reaction, the mixture was centrifuged, washed, and dried to obtain a composite cooling material.

[0066] Step 3: Dry nylon 56 in a vacuum drying oven at 105°C for 6 hours, vacuum dry ethylene-methyl acrylate-glycidyl methacrylate terpolymer at 50°C for 24 hours, and then mix nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polypentamethyleneguanidine hydrochloride, and composite cooling material in a ratio of 98:1:1.2:0.7.

[0067] The mixture was mixed in a mass ratio of 1.5 and 2.0, and extruded by a twin-screw extruder at a temperature of 260° C. and a rotation speed of 50 rpm, and pelletized to obtain mixed chips;

[0068] The mixed chips were vacuum dried at 105°C for 8 hours and then melt-spun at 285°C to obtain modified bio-based nylon 56 filaments; the modified bio-based nylon 56 filaments were woven into a 138 g / m 2 Bio-based nylon 56 fabric;

[0069] Step 4: Mix the composite modified boron nitride and ethanol in a mass ratio of 0.3:1, and ultrasonicate for 1.5 hours to obtain a finishing solution; spray the finishing solution on one side of the bio-based nylon 56 fabric at a spraying amount of 150g / m 2 , dry to get a cool, washable bio-based nylon 56 fabric.

[0070] The composite modified boron nitride used in the above Examples 2-4 is the composite modified boron nitride prepared in Example 1.

[0071] Comparative Example 1: Compared with Example 1, in the process of preparing the composite modified boron nitride in Comparative Example 1, surface modified boron nitride was used instead of antibacterial modified boron nitride, and other conditions remained unchanged.

[0072] Comparative Example 2: Compared with Example 4, in the process of preparing the bio-based nylon 56 fabric in Comparative Example 2, modified aluminum nitride microsheets were used instead of the composite cooling material, and other conditions remained unchanged.

[0073] Comparative Example 3: Compared with Example 4, in the process of preparing the bio-based nylon 56 fabric in Comparative Example 3, modified nano-alumina was used instead of the composite cooling material, and other conditions remained unchanged.

[0074] Comparative Example 4: Compared with Example 4, in the process of preparing the cool and washable bio-based nylon 56 fabric in Comparative Example 4, antibacterial modified boron nitride was used instead of composite modified boron nitride, and other conditions remained unchanged.

[0075] Comparative Example 5: Compared with Example 4, in the process of preparing the cool and washable bio-based nylon 56 fabric in Comparative Example 5, the composite modified boron nitride prepared in Comparative Example 1 was used, and other conditions remained unchanged.

[0076] In the above embodiments and comparative examples, the aluminum oxide nanoparticles are AKP-30 type α-Al2O3 nanoparticles (average particle size 100 nm), which are from Shanghai Buwei Applied Materials Technology Co., Ltd.; the aluminum nitride microflake powder is 3-5 μm in size and is from Qinhuangdao Yinuo High-tech Materials Development Co., Ltd.; the ethylene-methyl acrylate-glycidyl methacrylate terpolymer model is LOTADER® AX8900, E:MA:GMA=68:24:8 wt.%, produced by ARKEMA; the sodium carbonate-sodium bicarbonate buffer solution has a pH of 9.4 and is from Guangzhou Hewei Pharmaceutical Technology Co., Ltd.; the nylon 56, namely PA56, has a viscosity of 172.2 mL / g and is from Shanghai Kaisai Biotechnology R&D Center Co., Ltd.; the cellulose filter paper is a commercially available 102 type 100% cotton cellulose medium-speed qualitative filter paper provided by Hangzhou Special Paper Co., Ltd.; and hexagonal boron nitride (h-BN, 1 μm, ≥98.5%) is purchased from Beijing Yingnuo Chemical Technology Co., Ltd.

[0077] Experimental Example: Performance tests were performed on the cool, washable bio-based nylon 56 fabrics prepared in Examples 2-4 and Comparative Examples 2-5.

[0078] 1. Antibacterial performance test: The test was carried out in accordance with the international standard GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method", and the test bacteria were Escherichia coli and Staphylococcus aureus.

[0079] The test results are shown in Table 1:

[0080] Table 1

[0081]

[0082] The test results in Table 1 show that the cool, washable, bio-based nylon 56 fabrics produced in Examples 2-4 of the present invention have excellent antibacterial and washability properties. A comparison of Comparative Example 5 with Example 4 shows that the addition of glycidyl trimethyl chloride, which has antibacterial properties, to hexagonal boron nitride has a positive impact on improving the antibacterial properties of the cool, washable, bio-based nylon 56 fabrics.

[0083] 2. Moisture absorption performance test:

[0084] Moisture regain: The moisture regain of each group of samples was tested in accordance with the international standard GB / T 9995-1997 Textile materials - Determination of moisture content and moisture regain - Oven drying method to characterize the hygroscopic properties of each group of samples.

[0085] 3. Cooling performance:

[0086] Instant cooling performance test: In accordance with the international standard GB / T 35263-2017 "Test and evaluation standard for instant cooling performance of textiles", each group of samples was tested for instant cooling performance;

[0087] Contact continuous cooling performance test: Tested according to standard T CNGA 23-2021 "Testing and evaluation of the continuous cooling performance of clothing".

[0088] The test results are shown in Table 2:

[0089] Table 2

[0090]

[0091] It can be seen from the test results in Table 2 that the cool and washable bio-based nylon 56 fabrics prepared in Examples 2-4 of the present invention have good instantaneous coolness and continuous coolness, and excellent hygroscopicity. It can be seen from the comparison between Comparative Example 2 and Example 4 that the modified nano-alumina in the composite cool material improves the coolness performance of the bio-based nylon 56 fabric from the two perspectives of improving thermal conductivity and reducing solar energy absorption, and the hydrophilicity of the nano-alumina itself and the further improvement of the hydrophilicity after polydopamine modification have a positive effect on the improvement of the hygroscopicity of the bio-based nylon 56 fabric. In addition, the introduction of amino groups in polydopamine provides reactive groups for the grafting of the composite cool material with nylon 56 and ethylene-methyl acrylate-glycidyl methacrylate terpolymer, which makes the composite cool material decompose. The distribution is more uniform, thus playing a better role; from the comparison of comparative example 3 and embodiment 4, it can be seen that the modified aluminum nitride in the composite cooling material has good thermal conductivity, thereby improving the thermal conductivity of the composite cooling material; from the comparison of comparative example 4, comparative example 5 and embodiment 4, it can be seen that hexagonal boron nitride is modified in turn using glycidyl trimethyl ammonium chloride and 15-fluorooctanoyl chloride, glycidyl trimethyl ammonium chloride is helpful to improve the hygroscopicity of bio-based nylon 56 fabric, and 15-fluorooctanoyl chloride is helpful to the formation of wettability gradient on both sides of bio-based nylon 56 fabric, but it will cause its hygroscopicity to decrease.

[0092] 4. One-Way Moisture Transport Index (MMT): This is the fabric's ability to unidirectionally transport sweat discharged from the human body. The samples of Examples 2-4 were tested using the American standard AATCC195-2009 test standard and are divided into levels 1 to 5, with level 5 being the best. A level exceeding 3 is considered to have a unidirectional moisture transport effect.

[0093] The test results are shown in Table 3:

[0094] Table 3

[0095]

[0096] As shown in the test results of Table 3, the cool, washable bio-based nylon 56 fabrics prepared in Examples 2-4 of the present invention have good one-way moisture removal and sweat conduction performance due to the design of the wettability gradient on both sides. As shown in Comparative Example 2 and Example 4, the modified nano-alumina in the composite cool material has good hydrophilicity, improves the hydrophilicity of the bio-based nylon 56 fabric, increases the wettability difference on both sides of the cool, washable bio-based nylon 56 fabric, thereby improving the excellent one-way moisture removal and sweat conduction performance of the cool, washable bio-based nylon 56 fabric; As shown in Comparative Example 4 and Example 4, by spraying a finishing liquid containing composite modified boron nitride on one side of the bio-based nylon 56 fabric, the hydrophobic properties of the fluorine-containing hydrophobic link in the composite modified boron nitride form a significant wettability gradient on both sides of the bio-based nylon 56 fabric, so that the bio-based nylon 56 fabric has one-way moisture removal and sweat conduction performance.

[0097] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a cool, washable bio-based nylon 56 fabric, characterized in that: The following steps are involved: Step 1: reacting 1,5-pentanediamine with guanidine hydrochloride to obtain polypentamethyleneguanidine hydrochloride; Step 2: Aluminum oxide nanoparticles are modified with polydopamine to obtain modified nano-aluminum oxide; aluminum nitride microsheets are modified with γ-glycidyloxypropyltrimethoxysilane to obtain modified aluminum nitride microsheets; The modified nano-alumina is loaded on the modified aluminum nitride micro-sheets to obtain a composite cooling material; Step 3: nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polypentamethyleneguanidine hydrochloride, and the composite cooling material are blended and extruded, melt-spun, and then woven into a bio-based nylon 56 fabric; Wherein, the composite cool feeling material is prepared by the following method: The modified nano-alumina, modified aluminum nitride microsheets, and toluene are mixed in a mass ratio of (2-3):(10-16):(150-200), ultrasonicated at 200-300W for 10-20 minutes, then heated to 110-130°C in a nitrogen atmosphere, reacted for 3.5-4.5 hours, and after the reaction, centrifuged, washed, and dried to obtain a composite cooling material; Step 4: Mixing the composite modified boron nitride and ethanol to obtain a finishing solution; spraying the finishing solution on one side of the bio-based nylon 56 fabric, and drying to obtain a cool and washable bio-based nylon 56 fabric; The preparation method of the composite modified boron nitride comprises the following steps: Step S1, hexagonal boron nitride is modified with a silane coupling agent KH550 to obtain surface-modified boron nitride; Step S2, treating the surface-modified boron nitride with an antibacterial modification liquid containing glycidyl trimethylammonium chloride to obtain antibacterial modified boron nitride; Step S3: treating the antibacterial modified boron nitride with a fluorine-containing modification liquid containing pentadecafluorooctanoyl chloride to obtain composite modified boron nitride.

2. The method for preparing the cool and washable bio-based nylon 56 fabric according to claim 1, characterized in that: In the step 1, during the preparation of the polypentamethyleneguanidine hydrochloride, 1,5-pentanediamine and guanidine hydrochloride are mixed in equal molar ratios, and the reaction conditions are: first reacting at 115-125° C. for 1.5-2.5 hours, then heating to 190-210° C. for 5.5-7.5 hours, and the reaction by-product ammonia is absorbed with a 37% by mass aqueous hydrochloric acid solution.

3. The method for preparing the cool and washable bio-based nylon 56 fabric according to claim 1, characterized in that: In step 2, the preparation method of the modified nano-alumina is as follows: dopamine hydrochloride, Tris-HCl buffer with a pH of 8.5, and ethanol are mixed in a dosage ratio of (0.18-0.2) g: (150-180) mL: (50-60) mL to obtain a modification liquid; aluminum oxide nanoparticles are added to the modification liquid and soaked, stirred at 24-26° C. for 20-28 hours, filtered, washed, and dried to obtain modified nano-alumina; wherein the dosage ratio of the aluminum oxide nanoparticles to the modification liquid is (10-15) g: (100-120) mL.

4. The method for preparing the cool and washable bio-based nylon 56 fabric according to claim 1, characterized in that: In the step 2, the preparation method of the modified aluminum nitride microsheets is as follows: aluminum nitride microsheet powder and ethanol are mixed in a mass ratio of (6-10): (80-100), and ultrasonic treatment is performed for 20-40 minutes to obtain a mixed solution A; γ-glycidyloxypropyltrimethoxysilane and ethanol are mixed in a mass ratio of (0.5-0.8): (60-80), and stirred at 65-75°C for 4-6 hours to obtain a mixed solution B; under stirring conditions, the mixed solution A is added to the mixed solution B, the temperature is maintained at 65-75°C, and the stirring is carried out for 1.5-2.5 hours, and the modified aluminum nitride microsheets are obtained by filtering, washing, and drying.

5. The method for preparing the cool and washable bio-based nylon 56 fabric according to claim 1, characterized in that: In the step 3, the mass ratio of the nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polypentamethyleneguanidine hydrochloride, and the composite cooling material is 98:1:(1-1.5):(0.4-1).

6. The method for preparing the cool and washable bio-based nylon 56 fabric according to claim 1, characterized in that: In step 3, the blending extrusion conditions are: temperature 250-270°C, rotation speed 40-60rpm; melt spinning temperature 280-290°C; weight of bio-based nylon 56 fabric 120-150g / m 2 .

7. The method for preparing the cool and washable bio-based nylon 56 fabric according to claim 1, characterized in that: In the fourth step, the mass ratio of the composite modified boron nitride and ethanol is (0.2-0.4):1; the spraying amount of the finishing liquid is 140-160g / m 2 .

8. The method for preparing the cool and washable bio-based nylon 56 fabric according to claim 1, characterized in that: In the step 4, the preparation method of the composite modified boron nitride comprises the following steps: Step S1, dispersing hexagonal boron nitride in an 80% by mass ethanol aqueous solution, then adding a silane coupling agent KH550 thereto, stirring and reacting at 55-65° C. for 2-3 hours, filtering, washing, and drying to obtain surface-modified boron nitride; wherein the amount ratio of hexagonal boron nitride, ethanol aqueous solution, and silane coupling agent KH550 is (10-15) g: (100-120) mL: (1-3) g; Step S2, mixing equal volumes of deionized water and ethanol to form an ethanol aqueous solution; adding glycidyltrimethylammonium chloride to the ethanol aqueous solution to obtain an antibacterial modification liquid with a mass fraction of 5%; adding surface-modified boron nitride to the antibacterial modification liquid, adjusting the pH of the mixed system to 8.5 with sodium carbonate-sodium bicarbonate buffer, stirring and reacting at 38-42° C. for 7-9 hours, and after the reaction is completed, filtering, washing, and drying to obtain antibacterial modified boron nitride; wherein the mass ratio of surface-modified boron nitride to antibacterial modification liquid is (8-10):(100-150); Step S3, 15-fluorooctanoyl chloride and tetrahydrofuran are mixed in a mass ratio of (0.8-1.6): (15-20), and stirred in a nitrogen atmosphere for 1.5-2.5 hours to obtain a fluorine-containing modified liquid; the antibacterial modified boron nitride is dispersed in ethanol, and then mixed with the above-mentioned fluorine-containing modified liquid, stirred for reaction for 12-14 hours, and then a sodium bicarbonate aqueous solution with a mass fraction of 7.5% is added, the precipitate is collected by filtration, and dried to obtain a composite modified boron nitride; wherein the mass ratio of the antibacterial modified boron nitride, ethanol, fluorine-containing modified liquid, and sodium bicarbonate aqueous solution is (8-10): (80-100): (15.8-21.6): (2.1-4.2).

9. A cool and washable bio-based nylon 56 fabric prepared by the method for preparing a cool and washable bio-based nylon 56 fabric according to any one of claims 1 to 8.

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