Cool washing-resistant bio-based nylon 56 fabric and preparation method thereof

Abstract

The invention relates to the technical field of textiles, and discloses a cool and washable bio-based nylon 56 fabric and a preparation method thereof. The preparation method of the cool and washable bio-based nylon 56 fabric comprises the following steps: loading modified nano aluminum oxide on modified aluminum nitride microchips to obtain a composite cool material; nylon 56, an ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polypentamethylene guanidine hydrochloride and a composite cool feeling material are subjected to blending extrusion and melt spinning, and then the bio-based nylon 56 fabric is woven. Mixing the composite modified boron nitride and ethanol to obtain finishing liquid; spraying the finishing liquid on one side of the bio-based nylon 56 fabric, and drying to obtain the cool washable bio-based nylon 56 fabric. The cool and washable bio-based nylon 56 fabric disclosed by the invention has excellent cool feeling, antibacterial property, washable property, moisture absorption property and unidirectional perspiration property.

Description

Technical Field

[0001] The present invention relates to the technical field of textiles, and particularly to a cool-sensation and wash-resistant bio-based nylon 56 fabric and a preparation method thereof. Background Art

[0002] Nylon materials are widely used in fields such as clothing, automobiles, fishing gear, building materials, etc., and are closely related to people's daily lives. Nylon 6 is a common nylon material. However, the cool sensation of conventional nylon 6 fabrics or textiles is not persistent, and the hygroscopicity is poor. Moreover, all nylon 6 raw materials come from petroleum. With the gradual depletion of petroleum resources and the increasing global environmental awareness, environmentally friendly bio-based PA56 (nylon 56) prepared by bioconversion of 1,5-pentanediamine (PDA) has attracted wide attention.

[0003] PA56 fabrics have good dyeing, softness and antistatic properties. In addition, their good hygroscopicity provides great opportunities for textiles. However, the cool sensation and antibacterial properties of PA56 fabrics need to be improved, especially in the hot summer, which cannot meet people's requirements for the wearing comfort, health and safety of clothing. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a preparation method of a cool-sensation and wash-resistant bio-based nylon 56 fabric, including the following steps: Step 1: React 1,5-pentanediamine with guanidine hydrochloride to obtain polyhexamethylene guanidine hydrochloride; Step 2: Modify alumina nanoparticles with polydopamine to obtain modified nano-alumina; modify aluminum nitride microplates with γ-glycidoxypropyltrimethoxysilane to obtain modified aluminum nitride microplates; load the modified nano-alumina on the modified aluminum nitride microplates to obtain a composite cool-sensation material; Step 3: Blend and extrude nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polyhexamethylene guanidine hydrochloride, and the composite cool-sensation material, and then perform melt spinning and weaving to form a bio-based nylon 56 fabric; Step 4: Mix composite modified boron nitride and ethanol to obtain a finishing solution; spray the finishing solution on one side of the bio-based nylon 56 fabric and dry to obtain a cool-sensation and wash-resistant bio-based nylon 56 fabric; Wherein, the preparation method of the composite modified boron nitride includes the following steps: Step S1: Modify hexagonal boron nitride with silane coupling agent KH550 to obtain surface-modified boron nitride; Step S2: Treat the surface-modified boron nitride with an antibacterial modification solution containing glycidyltrimethylammonium chloride to obtain antibacterial modified boron nitride; Step S3: Treat the antibacterial modified boron nitride with a fluorine-containing modification solution containing pentadecafluorooctanoyl chloride to obtain composite modified boron nitride.

[0005] Preferably, in the first step, during the preparation of the poly (pentamethylene guanidine hydrochloride): 1,5-pentanediamine and guanidine hydrochloride are mixed in an equimolar ratio, and the reaction conditions are as follows: first, react at 115 - 125 °C for 1.5 - 2.5 h, then raise the temperature to 190 - 210 °C and react for 5.5 - 7.5 h. The by-product ammonia of the reaction is absorbed by a hydrochloric acid aqueous solution with a mass fraction of 37%. Preferably, in the second step, the preparation method of the modified nano-aluminum oxide: Mix dopamine hydrochloride, Tris-HCl buffer solution with a pH of 8.5, and ethanol in a dosage ratio of (0.18 - 0.2) g : (150 - 180) mL : (50 - 60) mL to obtain a modified solution; add alumina nanoparticles to the modified solution for soaking treatment, stir at 24 - 26 °C for 20 - 28 h, filter, wash, and dry to obtain modified nano-aluminum oxide; wherein, the dosage ratio of alumina nanoparticles to the modified solution is (10 - 15) g : (100 - 120) mL. In the above process: Under alkaline conditions, dopamine polymerizes on the surface of alumina nanoparticles to form polydopamine, and modified nano-aluminum oxide is obtained.

[0006] Preferably, in the second step, the preparation method of the modified aluminum nitride microplate: Mix aluminum nitride microplate powder and ethanol in a mass ratio of (6 - 10) : (80 - 100), and perform ultrasonic treatment for 20 - 40 min to obtain a mixed solution A; mix γ-glycidyl ether oxypropyltrimethoxysilane and ethanol in a mass ratio of (0.5 - 0.8) : (60 - 80), and stir at 65 - 75 °C for 4 - 6 h to obtain a mixed solution B; under stirring conditions, add the mixed solution A to the mixed solution B, keep the temperature at 65 - 75 °C and stir for 1.5 - 2.5 h, filter, wash, and dry to obtain modified aluminum nitride microplates. In the above process: γ-Glycidyl ether oxypropyltrimethoxysilane modifies the aluminum nitride microplate and introduces epoxy groups on its surface.

[0007] Preferably, in the second step, the preparation method of the composite cool-sensation material: Mix the modified nano-aluminum oxide, modified aluminum nitride microplates, and toluene in a mass ratio of (2 - 3) : (10 - 16) : (150 - 200), perform ultrasonic treatment for 10 - 20 min under the condition of 200 - 300 W, then heat to 110 - 130 °C in a nitrogen atmosphere and react for 3.5 - 4.5 h. After the reaction, centrifuge, wash, and dry to obtain the composite cool-sensation material. In the above process: The amino group on the surface of polydopamine on the surface of the modified nano-aluminum oxide reacts with the epoxy group on the surface of the modified aluminum nitride microplate, and the modified nano-aluminum oxide is loaded on the modified aluminum nitride microplate.

[0008] Preferably, in the third step, the mass ratio of the nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, poly(pentamethylene guanidine) hydrochloride, and the composite cool feeling material is 98:1:(1 - 1.5):(0.4 - 1).

[0009] Preferably, in the third step, the conditions for melt blending and extrusion are as follows: the temperature is 250 - 270 °C, the rotation speed is 40 - 60 rpm; the melt spinning temperature is 280 - 290 °C; the gram weight of the bio-based nylon 56 fabric is 120 - 150 g / m 2 .

[0010] Preferably, in the fourth step, the mass ratio of the composite modified boron nitride to ethanol is (0.2 - 0.4):1; the spraying amount of the finishing solution is 140 - 160 g / m 2 .

[0011] Furthermore, in the fourth step, the preparation method of the composite modified boron nitride includes the following steps: Step S1: Disperse hexagonal boron nitride in an ethanol aqueous solution with a mass fraction of 80%, then add silane coupling agent KH550 thereto, and stir and react at 55 - 65 °C for 2 - 3 h, filter, wash, and dry to obtain surface-modified boron nitride; wherein, the dosage ratio of hexagonal boron nitride, ethanol aqueous solution, and silane coupling agent KH550 is (10 - 15) g:(100 - 120) mL:(1 - 3) g; In the above process: The hexagonal boron nitride is modified by silane coupling agent KH550, and a large number of amino groups are introduced on its surface; Step S2: Mix deionized water and ethanol in equal volume to form an ethanol aqueous solution; add glycidyl trimethyl ammonium chloride to the above ethanol aqueous solution to obtain an antibacterial modification solution with a mass fraction of 5%; add the surface-modified boron nitride to the above antibacterial modification solution, adjust the pH of the mixed system to 8.5 with a sodium carbonate-sodium bicarbonate buffer solution, stir and react at 38 - 42 °C for 7 - 9 h, after the reaction is completed, filter, wash, and dry to obtain antibacterial modified boron nitride; wherein, the mass ratio of the surface-modified boron nitride to the antibacterial modification solution is (8 - 10):(100 - 150); In the above process: The epoxy group of glycidyl trimethyl ammonium chloride reacts with some amino groups on the surface-modified boron nitride, and a quaternary ammonium salt structure with antibacterial effect is introduced on the boron nitride; Step S3: Mix perfluorooctanoyl chloride and tetrahydrofuran at a mass ratio of (0.8 - 1.6):(15 - 20), stir for 1.5 - 2.5 h in a nitrogen atmosphere to obtain a fluorine-modified liquid; Disperse the antibacterial modified boron nitride in ethanol, then mix it with the above-mentioned fluorine-modified liquid, stir and react for 12 - 14 h, then add an aqueous sodium bicarbonate solution with a mass fraction of 7.5%, filter by suction to collect the precipitate, and dry to obtain the composite modified boron nitride; Among them, the mass ratio of the antibacterial modified boron nitride, ethanol, fluorine-modified liquid, and aqueous sodium bicarbonate solution is (8 - 10):(80 - 100):(15.8 - 21.6):(2.1 - 4.2); In the above process: The acyl chloride group in perfluorooctanoyl chloride reacts with some 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.

[0012] The cool-sensation and wash-resistant bio-based nylon 56 fabric prepared by using the preparation method of the cool-sensation and wash-resistant bio-based nylon 56 fabric.

[0013] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. The present invention replaces the traditional petroleum-based nylon fabric with a bio-based nylon 56 fabric, reducing the use of fossil raw materials and being more environmentally friendly.

[0014] 2. The present invention blends and extrudes nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, poly(pentamethylene guanidine) hydrochloride, and a composite cool-sensation material, then melts and spins them and weaves them into a bio-based nylon 56 fabric; Poly(pentamethylene guanidine) hydrochloride is used as a bio-based antibacterial agent, endowing the bio-based nylon 56 fabric with excellent antibacterial properties; The presence of epoxy groups in the ethylene-methyl acrylate-glycidyl methacrylate terpolymer enables poly(pentamethylene guanidine) hydrochloride and the composite cool-sensation material to be grafted onto nylon 56 in the form of chemical bonds, improving the compatibility of poly(pentamethylene guanidine) hydrochloride and the composite cool-sensation material with nylon 56, enhancing the mechanical properties of the bio-based nylon 56 fabric, and more importantly, enabling the bio-based nylon 56 fabric to maintain long-lasting cool-sensation and antibacterial properties; Furthermore, the composite cool-sensation material of the present invention is prepared by loading modified nano-aluminum oxide on modified aluminum nitride micro-sheets. Both nano-aluminum oxide and aluminum nitride are inorganic materials with excellent thermal conductivity. Loading the modified nano-aluminum oxide on the modified aluminum nitride micro-sheets helps to form more thermal conduction networks, making the composite cool-sensation material have better thermal conductivity. Moreover, nano-aluminum oxide also has good sunlight reflection ability, which can reduce the absorption of sunlight. Starting from both thermal conduction and sunlight reflection, the cool-sensation of the bio-based nylon 56 fabric is improved. In addition, nano-aluminum oxide also has good hydrophilic properties. After being modified with polydopamine, its hydrophilicity is further enhanced, thereby improving the moisture absorption and breathability of the bio-based nylon 56 fabric. The introduction of amino groups in polydopamine provides reactive groups for the grafting of the composite cool-sensation material with nylon 56 and ethylene-methyl acrylate-glycidyl methacrylate terpolymer, making the composite cool-sensation material more evenly dispersed, so as to exert better effects.

[0015] 3. The present invention modifies hexagonal boron nitride with silane coupling agent KH550, glycidyl trimethyl ammonium chloride, and pentadecafluorooctanoyl chloride in sequence to obtain composite modified boron nitride. Hexagonal boron nitride is an inorganic material with good thermal conductivity. By grafting glycidyl trimethyl ammonium chloride with antibacterial properties and fluorinated hydrophobic chains on hexagonal boron nitride, and then spraying the finishing solution containing the composite modified boron nitride on one side of the bio-based nylon 56 fabric, the antibacterial property and cool-sensation of the bio-based nylon 56 fabric are improved, and a significant wetting gradient is formed on both sides of the bio-based nylon 56 fabric. When wearing, the hydrophobic side contacts the skin to achieve unidirectional and rapid evaporation of sweat, keep the skin cool, reduce skin stickiness, and thus improve the thermal and moisture comfort of wearing. Brief Description of the Drawings

[0016] Figure 1 is the process flow chart of the preparation method of the cool-sensation and wash-resistant bio-based nylon 56 fabric of the present invention; Figure 2 is the antibacterial property test comparison chart of the cool-sensation and wash-resistant bio-based nylon 56 fabric prepared in Examples 2-4 and Comparative Examples 2-5 of the present invention before and after washing; Figure 3 is the moisture regain test comparison chart of the cool-sensation and wash-resistant bio-based nylon 56 fabric prepared in Examples 2-4 and Comparative Examples 2-5 of the present invention. Detailed Embodiments

[0017] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a 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 those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0018] Example 1: This example discloses a preparation method of composite modified boron nitride, which includes the following steps: Step S1: Disperse 12.5 g of hexagonal boron nitride in 110 mL of an ethanol aqueous solution with a mass fraction of 80%, then add 2 g of silane coupling agent KH550 thereto, stir and react at 60 °C for 2.5 h, filter, wash, and dry to obtain surface-modified boron nitride; Step S2: Mix deionized water and ethanol in equal volume to form an ethanol aqueous solution; add glycidyltrimethylammonium chloride to the above ethanol aqueous solution to obtain an antibacterial modification solution with a mass fraction of 5%; add 9 g of surface-modified boron nitride to 125 g of the above antibacterial modification solution, adjust the pH of the mixed system to 8.5 with a sodium carbonate-sodium bicarbonate buffer solution, stir and react at 40 °C for 8 h, after the reaction ends, filter, wash, and dry to obtain antibacterial modified boron nitride; Step S3: Add 1.2 g of pentafluorooctanoyl chloride to 17.5 g of tetrahydrofuran, stir in a nitrogen atmosphere for 2 h to obtain a fluorine-containing modification solution; disperse 9 g of antibacterial modified boron nitride in 90 g of ethanol, then mix it with the above fluorine-containing modification solution, stir and react for 13 h, then add 3.3 g of a sodium bicarbonate aqueous solution with a mass fraction of 7.5%, filter by suction to collect the precipitate, and dry to obtain composite modified boron nitride.

[0019] Example 2: This example discloses a preparation method of a cool-sensation and washable bio-based nylon 56 fabric, which includes the following steps: Step 1: Mix 1,5-pentanediamine and guanidine hydrochloride in an equimolar ratio, first react at 115 °C for 2.5 h, then raise the temperature to 190 °C and react for 7.5 h, absorb the by-product ammonia with a hydrochloric acid aqueous solution with a mass fraction of 37%, after the reaction ends, vacuum-dry the obtained product at 75 °C for 50 h to obtain poly(pentamethylene guanidine hydrochloride); Step 2: Mix 0.18 g of dopamine hydrochloride, 150 mL of Tris-HCl buffer solution with a pH of 8.5, and 50 mL of ethanol to obtain a modification solution; add 10 g of alumina nanoparticles to 100 mL of the modification solution for soaking treatment, stir at 24 °C for 28 h, filter with a cellulose filter paper, and wash 3 times with deionized water, vacuum-dry at 55 °C to obtain modified nano-alumina; Add 6 g of aluminum nitride microplate powder to 80 g of ethanol, ultrasonically treat for 20 min to obtain a mixed solution A; add 0.5 g of γ-glycidoxypropyltrimethoxysilane to 60 g of ethanol, stir the mixture at 65 °C for 6 h to obtain a mixed solution B; under stirring conditions, add the mixed solution A to the mixed solution B, keep the temperature at 65 °C and stir for 2.5 h, filter, wash, and dry to obtain modified aluminum nitride microplates; Add 3 g of modified nano-aluminum oxide and 16 g of modified aluminum nitride microplates to 150 g of toluene, ultrasonically treat for 20 min under the condition of 200 W, then heat to 110 °C in a nitrogen atmosphere and react for 4.5 h. After the reaction, centrifuge, wash, and dry to obtain a composite cool-sensation material; Step 3: Dry nylon 56 in a vacuum drying oven at 100 °C for 7 h, and dry ethylene-methyl acrylate-glycidyl methacrylate terpolymer in a vacuum at 45 °C for 28 h. Then mix nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, poly (pentamethylene guanidine hydrochloride), and the composite cool-sensation material in a mass ratio of 98:1:1:0.4, and co-extrude and pelletize using a twin-screw extruder under the conditions of a temperature of 250 °C and a rotation speed of 40 rpm to obtain mixed chips; Vacuum-dry the mixed chips at 100 °C for 10 h, and then melt-spin at 280 °C to obtain modified bio-based nylon 56 filaments; Weave the modified bio-based nylon 56 filaments into a bio-based nylon 56 fabric with a grammage of 120 g / m 2 ; Step 4: Mix composite modified boron nitride and ethanol in a mass ratio of 0.2:1, and ultrasonically treat for 1 h to obtain a finishing solution; Spray the finishing solution on one side of the bio-based nylon 56 fabric, with a spraying amount of 150 g / m 2 , and dry to obtain a cool-sensation and washable bio-based nylon 56 fabric.

[0020] Example 3: This example discloses a preparation method of a cool-sensation and washable bio-based nylon 56 fabric, including the following steps: Step 1: Mix 1,5-pentanediamine and guanidine hydrochloride in an equimolar ratio, first react at 125 °C for 1.5 h, then raise the temperature to 210 °C and react for 5.5 h. Absorb the by-product ammonia of the reaction with a 37% hydrochloric acid aqueous solution. After the reaction, vacuum-dry the obtained product at 80 °C for 45 h to obtain poly (pentamethylene guanidine hydrochloride); Step 2: Mix 0.2 g of dopamine hydrochloride, 180 mL of Tris-HCl buffer solution with a pH of 8.5, and 60 mL of ethanol to obtain a modification solution; Add 15 g of alumina nanoparticles to 120 mL of the modification solution for immersion treatment, stir at 26 °C for 20 h, filter with a cellulose filter paper, wash 5 times with deionized water, and vacuum-dry at 65 °C to obtain modified nano-aluminum oxide; Add 10 g of aluminum nitride microplate powder to 100 g of ethanol, and ultrasonically treat for 40 min to obtain a mixed solution A; Add 0.8 g of γ-glycidoxypropyltrimethoxysilane to 80 g of ethanol, and stir the mixture at 75 °C for 6 h to obtain a mixed solution B; Under stirring conditions, add the mixed solution A to the mixed solution B, and keep stirring at 75 °C for 2.5 h, filter, wash, and dry to obtain modified aluminum nitride microplates; Add 3 g of modified nano-aluminum oxide and 16 g of modified aluminum nitride microplates to 200 g of toluene, ultrasonically treat for 10 min under the condition of 300 W, then heat to 130 °C in a nitrogen atmosphere and react for 3.5 h. After the reaction, centrifuge, wash, and dry to obtain a composite cool-sensation material; Step 3: Dry nylon 56 in a vacuum drying oven at 110 °C for 5 h, and dry ethylene-methyl acrylate-glycidyl methacrylate terpolymer in a vacuum at 55 °C for 20 h. Then mix nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, poly (pentamethylene guanidine hydrochloride), and the composite cool-sensation material in a mass ratio of 98:1:1.5:1, and co-extrude and pelletize with a twin-screw extruder under the conditions of a temperature of 270 °C and a rotation speed of 60 rpm to obtain mixed chips; Vacuum-dry the mixed chips at 105 °C for 8 h, and then melt-spin at 290 °C to obtain modified bio-based nylon 56 filaments; Weave the modified bio-based nylon 56 filaments into a bio-based nylon 56 fabric with a grammage of 150 g / m 2 ; Step 4: Mix composite modified boron nitride and ethanol in a mass ratio of 0.4:1, and ultrasonically treat for 2 h to obtain a finishing solution; Spray the finishing solution on one side of the bio-based nylon 56 fabric, with a spraying amount of 150 g / m 2 , and dry to obtain a cool-sensation and wash-resistant bio-based nylon 56 fabric.

[0021] Example 4: This example discloses a preparation method of a cool-sensation and wash-resistant bio-based nylon 56 fabric, including the following steps: Step 1: Mix 1,5-pentanediamine and guanidine hydrochloride in an equimolar ratio, first react at 120 °C for 2 h, then raise the temperature to 200 °C and react for 6.5 h. Absorb the by-product ammonia of the reaction with a 37% hydrochloric acid aqueous solution. After the reaction, vacuum-dry the obtained product at 78 °C for 48 h to obtain poly (pentamethylene guanidine hydrochloride); Step 2: Mix 0.19 g of dopamine hydrochloride, 175 mL of Tris-HCl buffer solution with a pH of 8.5, and 55 mL of ethanol to obtain a modification solution; Add 12.5 g of alumina nanoparticles to 110 mL of the modification solution for soaking treatment, stir at 25 °C for 24 h, filter with a cellulose filter paper, wash 4 times with deionized water, and vacuum-dry at 60 °C to obtain modified nano-aluminum oxide; 8 g of aluminum nitride microplate powder was added to 90 g of ethanol, and the mixture was ultrasonically treated for 30 min to obtain a mixed solution A; 0.7 g of γ-glycidoxypropyltrimethoxysilane was added to 70 g of ethanol, and the mixture was stirred at 70 °C for 5 h to obtain a mixed solution B; under stirring conditions, the mixed solution A was added to the mixed solution B, and the temperature was maintained at 70 °C and stirred for 2 h, followed by filtration, washing, and drying to obtain modified aluminum nitride microplates; 2.5 g of modified nano-aluminum oxide and 13 g of modified aluminum nitride microplates were added to 175 g of toluene, and the mixture was ultrasonically treated for 15 min under the condition of 250 W, and then heated to 120 °C in a nitrogen atmosphere and reacted for 4 h. After the reaction, centrifugation, washing, and drying were carried out to obtain a composite cool feeling material; Step 3: Nylon 56 was dried in a vacuum drying oven at 105 °C for 6 h, and ethylene-methyl acrylate-glycidyl methacrylate terpolymer was dried in vacuo at 50 °C for 24 h. Then, nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, poly (pentamethylene guanidine hydrochloride), and the composite cool feeling material were mixed at a mass ratio of 98:1:1.2:0.7 and melt-blended and pelletized using a twin-screw extruder under the conditions of a temperature of 260 °C and a rotation speed of 50 rpm to obtain mixed pellets; The mixed pellets were dried in vacuo at 105 °C for 8 h, 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 bio-based nylon 56 fabric with a grammage of 138 g / m 2 ; Step 4: Composite modified boron nitride and ethanol were mixed at a mass ratio of 0.3:1 and ultrasonically treated for 1.5 h to obtain a finishing solution; the finishing solution was sprayed on one side of the bio-based nylon 56 fabric, and the spraying amount was 150 g / m 2 , and then dried to obtain a cool feeling and washable bio-based nylon 56 fabric.

[0022] The composite modified boron nitride used in the above Examples 2-4 was the composite modified boron nitride prepared in Example 1.

[0023] 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.

[0024] 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 microplates were used instead of the composite cool feeling material, and other conditions remained unchanged.

[0025] Comparative Example 3: Compared with Example 4, in the process of preparing the bio-based nylon 56 fabric in Comparative Example 3, modified nano-aluminum oxide was used instead of the composite cool feeling material, and other conditions remained unchanged.

[0026] Comparative Example 4: Compared with Example 4, in the process of preparing the cool-sensation and wash-resistant bio-based nylon 56 fabric, antibacterial modified boron nitride was used instead of composite modified boron nitride, and other conditions remained unchanged.

[0027] Comparative Example 5: Compared with Example 4, in the process of preparing the cool-sensation and wash-resistant bio-based nylon 56 fabric, the composite modified boron nitride prepared in Comparative Example 1 was used, and other conditions remained unchanged.

[0028] In the above examples and comparative examples, the alumina nanoparticles were AKP-30 type α-Al2O3 nanoparticles (average particle size 100 nm), from Shanghai Buwei Applied Materials Technology Co., Ltd.; the aluminum nitride microplate powder, with a size of 3 - 5 μm, from Qinhuangdao Yinuo High-Tech Materials Development Co., Ltd.; the ethylene-methyl acrylate-glycidyl methacrylate terpolymer was of the LOTADER® AX8900 type, E:MA:GMA = 68:24:8 wt.%, produced by ARKEMA; the sodium carbonate-sodium bicarbonate buffer solution, with a pH of 9.4, from Guangzhou Hewei Medical Technology Co., Ltd.; nylon 56, namely PA56, with a viscosity of 172.2 mL / g, from Shanghai Kaisai Biotechnology R & D Center Co., Ltd.; the cellulose filter paper was a commercially available No. 102 type 100% cotton cellulose medium-speed qualitative filter paper, provided by Hangzhou Special Paper Co., Ltd.; hexagonal boron nitride (h-BN, 1 μm, ≥98.5%) was purchased from Beijing Innochem Technology Co., Ltd.

[0029] Experimental Example: Performance tests were carried out on the cool-sensation and wash-resistant bio-based nylon 56 fabrics prepared in Examples 2 - 4 and Comparative Examples 2 - 5.

[0030] I. Antibacterial performance test: It was determined in accordance with the international standard GB / T20944.3 - 2008 "Evaluation of antibacterial properties of textiles - Part 3: Oscillation method", and the test strains were Escherichia coli and Staphylococcus aureus.

[0031] The test results are shown in Table 1: Table 1

[0032] From the test results in Table 1, it can be seen that the cool-sensation and wash-resistant bio-based nylon 56 fabrics prepared in Examples 2 - 4 of the present invention have excellent antibacterial properties and wash-resistant properties. From the comparison between Comparative Example 5 and Example 4, it can be seen that grafting glycidyltrimethylammonium chloride with antibacterial properties onto hexagonal boron nitride has a positive effect on improving the antibacterial properties of the cool-sensation and wash-resistant bio-based nylon 56 fabric.

[0033] II. Moisture absorption performance test: Moisture regain: The moisture regain of each group of samples was tested according to the international standard GB / T 9995-1997 "Textiles - Determination of moisture content and moisture regain - Oven drying method" to characterize the moisture absorption performance of each group of samples.

[0034] III. Cooling sensation performance: Instantaneous cooling sensation performance test: The instantaneous cooling sensation test in contact with each group of samples was carried out according to the international standard GB / T 35263-2017 "Testing and evaluation standard for the instantaneous cooling sensation performance of textiles in contact". Continuous cooling sensation performance test in contact: The test was carried out according to the standard T CNGA 23-2021 "Clothing - Detection and evaluation of continuous cooling sensation performance in contact".

[0035] The test results are shown in Table 2: Table 2

[0036] It can be seen from the test results in Table 2 that the cooling-sensation wash-resistant bio-based nylon 56 fabric prepared in Examples 2-4 of the present invention has good instantaneous cooling sensation and continuous cooling sensation, and excellent moisture absorption performance. From the comparison between Comparative Example 2 and Example 4, it can be known that the modified nano-aluminum oxide in the composite cooling-sensation material improves the cooling-sensation performance of the bio-based nylon 56 fabric from two aspects of increasing the thermal conductivity coefficient and reducing solar energy absorption. In addition, the hydrophilicity of nano-aluminum oxide itself and the further improvement of hydrophilicity after polydopamine modification have a positive impact on the improvement of the moisture absorption of the bio-based nylon 56 fabric. Moreover, the introduction of amino groups in polydopamine provides reactive groups for the grafting of the composite cooling-sensation material with nylon 56 and ethylene-methyl acrylate-glycidyl methacrylate terpolymer, making the composite cooling-sensation material more evenly dispersed, thus exerting better efficacy. From the comparison between Comparative Example 3 and Example 4, it can be known that the modified aluminum nitride in the composite cooling-sensation material has high thermal conductivity, improving the thermal conductivity performance of the composite cooling-sensation material. From the comparison between Comparative Example 4, Comparative Example 5 and Example 4, it can be known that using glycidyltrimethylammonium chloride and pentadecafluorooctanoyl chloride to modify hexagonal boron nitride in sequence, glycidyltrimethylammonium chloride helps to improve the moisture absorption of the bio-based nylon 56 fabric, while pentadecafluorooctanoyl chloride helps to form a wetting gradient on both sides of the bio-based nylon 56 fabric, but will lead to a decrease in its moisture absorption.

[0037] IV. Unidirectional transport index (MMT): It is the unidirectional transport ability of the fabric to the sweat discharged by the human body. The samples of Examples 2-4 were tested according to the American standard AATCC195-2009 test standard, which is divided into levels 1-5, with level 5 being the best. If it exceeds level 3, it is considered to have a unidirectional moisture conduction effect.

[0038] The test results are shown in Table 3: Table 3

[0039] As can be seen from the test results in Table 3, due to the design of the wettability gradient on both sides, the cool-sensation and wash-resistant bio-based nylon 56 fabric prepared in Examples 2-4 of the present invention has excellent one-way moisture wicking and sweat conduction performance. From the comparison between Comparative Example 2 and Example 4, it can be seen that the modified nano-aluminum oxide in the composite cool-sensation material has good hydrophilicity, which improves the hydrophilicity of the bio-based nylon 56 fabric, increases the wettability difference between both sides of the cool-sensation and wash-resistant bio-based nylon 56 fabric, and thus improves the excellent one-way moisture wicking and sweat conduction performance of the cool-sensation and wash-resistant bio-based nylon 56 fabric; from the comparison between Comparative Example 4 and Example 4, it can be seen that by spraying a finishing solution containing composite modified boron nitride on one side of the bio-based nylon 56 fabric, the hydrophobic property of the fluorine-containing hydrophobic chain in the composite modified boron nitride forms a significant wetting gradient on both sides of the bio-based nylon 56 fabric, making the bio-based nylon 56 fabric have one-way moisture wicking and sweat conduction performance.

[0040] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method of a cool-sensation and wash-resistant bio-based nylon 56 fabric, characterized in that, It includes the following steps: Step 1: 1,5-pentanediamine reacts with guanidine hydrochloride to obtain polyhexamethylene guanidine hydrochloride; Step 2: Alumina nanoparticles are modified with polydopamine to obtain modified nano-alumina; aluminum nitride microplates are modified with γ-glycidoxypropyltrimethoxysilane to obtain modified aluminum nitride microplates; The modified nano-alumina is loaded on the modified aluminum nitride microplates to obtain a composite cool-sensation material; Step 3: Nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polyhexamethylene guanidine hydrochloride, and the composite cool-sensation material are blended, extruded, melt-spun, and then woven into a bio-based nylon 56 fabric; Step 4: The composite modified boron nitride and ethanol are mixed to obtain a finishing solution; the finishing solution is sprayed on one side of the bio-based nylon 56 fabric and dried to obtain a cool-sensation and wash-resistant bio-based nylon 56 fabric; Among them, the preparation method of the composite modified boron nitride includes the following steps: Step S1: Hexagonal boron nitride is modified with silane coupling agent KH550 to obtain surface-modified boron nitride; Step S2: The surface-modified boron nitride is treated with an antibacterial modification solution containing glycidyltrimethylammonium chloride to obtain antibacterial modified boron nitride; Step S3: The antibacterial modified boron nitride is treated with a fluorine-containing modification solution containing pentadecafluorooctanoyl chloride to obtain the composite modified boron nitride.

2. The preparation method of the cool-sensation washable bio-based nylon 56 fabric according to claim 1, wherein In the above Step 1, during the preparation process of the polyhexamethylene guanidine hydrochloride: 1,5-pentanediamine and guanidine hydrochloride are mixed in an equimolar ratio, and the reaction conditions are: first react at 115-125 °C for 1.5-2.5 h, then raise the temperature to 190-210 °C and react for 5.5-7.5 h, and the by-product ammonia is absorbed with a 37% hydrochloric acid aqueous solution by mass fraction.

3. The preparation method of the cool-sensation wash-resistant bio-based nylon 56 fabric according to claim 1, characterized in that, In the above Step 2, the preparation method of the modified nano-alumina: Dopamine hydrochloride, Tris-HCl buffer solution 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 solution; the alumina nanoparticles are added to the modification solution for soaking treatment, stirred at 24-26 °C for 20-28 h, filtered, washed, and dried to obtain the modified nano-alumina; among them, the dosage ratio of the alumina nanoparticles to the modification solution is (10-15) g:(100-120) mL.

4. The preparation method of the cool-sensation wash-resistant bio-based nylon 56 fabric according to claim 1, wherein, In the above Step 2, the preparation method of the modified aluminum nitride microplates: Aluminum nitride microplate powder and ethanol are mixed in a mass ratio of (6-10):(80-100), ultrasonically treated for 20-40 min to obtain a mixed solution A; γ-glycidoxypropyltrimethoxysilane and ethanol are mixed in a mass ratio of (0.5-0.8):(60-80), stirred at 65-75 °C for 4-6 h to obtain a mixed solution B; under stirring conditions, the mixed solution A is added to the mixed solution B, and stirred at 65-75 °C for 1.5-2.5 h, filtered, washed, and dried to obtain the modified aluminum nitride microplates.

5. The preparation method of the cool-sensation wash-resistant bio-based nylon 56 fabric according to claim 1, characterized in that, In the second step, the preparation method of the composite cool-sensation material: Mix modified nano-aluminum oxide, modified aluminum nitride micro-sheets, and toluene in a mass ratio of (2-3):(10-16):(150-200), ultrasonically treat for 10-20 min under the condition of 200-300 W, then heat to 110-130 °C in a nitrogen atmosphere and react for 3.5-4.5 h. After the reaction, centrifuge, wash, and dry to obtain the composite cool-sensation material.

6. The preparation method of the cool-sensation washable bio-based nylon 56 fabric according to claim 1, wherein, In the third step, the mass ratio of the nylon 56, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, poly(pentamethylene guanidine) hydrochloride, and the composite cool-sensation material is 98:1:(1-1.5):(0.4-1).

7. The preparation method of the cool-sensation wash-resistant bio-based nylon 56 fabric according to claim 1, characterized in that, In the third step, the conditions for melt blending and extrusion are as follows: the temperature is 250-270°C, the rotation speed is 40-60 rpm; the melt spinning temperature is 280-290°C; the gram weight of the bio-based nylon 56 fabric is 120-150 g / m 2 .

8. The preparation method of the cool-sensation wash-resistant bio-based nylon 56 fabric according to claim 1, wherein In the fourth step, the mass ratio of the composite modified boron nitride to ethanol is (0.2 - 0.4):1; the spraying amount of the finishing liquid is 140 - 160 g / m 2 .

9. The preparation method of the cool-sensation washable bio-based nylon 56 fabric according to claim 1, wherein, In the fourth step, the preparation method of the composite modified boron nitride includes the following steps: Step S1: Disperse hexagonal boron nitride in an ethanol aqueous solution with a mass fraction of 80%, then add silane coupling agent KH550 thereto, stir and react at 55-65 °C for 2-3 h, filter, wash, and dry to obtain surface-modified boron nitride; wherein, the dosage 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: Mix deionized water and ethanol in equal volume to form an ethanol aqueous solution; add glycidyltrimethylammonium chloride to the above ethanol aqueous solution to obtain an antibacterial modification solution with a mass fraction of 5%; add the surface-modified boron nitride to the above antibacterial modification solution, adjust the pH of the mixed system to 8.5 with a sodium carbonate-sodium bicarbonate buffer solution, stir and react at 38-42 °C for 7-9 h. After the reaction, filter, wash, and dry to obtain antibacterial-modified boron nitride; wherein, the mass ratio of the surface-modified boron nitride to the antibacterial modification solution is (8-10):(100-150); Step S3: Mix pentadecafluorooctanoyl chloride and tetrahydrofuran in a mass ratio of (0.8-1.6):(15-20), stir in a nitrogen atmosphere for 1.5-2.5 h to obtain a fluorine-containing modification solution; disperse the antibacterial-modified boron nitride in ethanol, then mix it with the above fluorine-containing modification solution, stir and react for 12-14 h, then add a sodium bicarbonate aqueous solution with a mass fraction of 7.5%, filter and collect the precipitate, and dry to obtain the composite modified boron nitride; wherein, the mass ratio of the antibacterial-modified boron nitride, ethanol, fluorine-containing modification solution, and sodium bicarbonate aqueous solution is (8-10):(80-100):(15.8-21.6):(2.1-4.2).

10. A cool-sensation and wash-resistant bio-based nylon 56 fabric prepared by using the preparation method of the cool-sensation and wash-resistant bio-based nylon 56 fabric according to any one of claims 1-9.

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