Self-cleaning antifouling fabric and preparation method thereof

Abstract

The invention discloses a self-cleaning antifouling fabric and a preparation method thereof, and relates to the field of textile fabrics. When the self-cleaning antifouling fabric is prepared, hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine and diethyl vinyl phosphate are subjected to a reaction, and pre-modified multi-walled carbon nanotubes are obtained; reacting the pre-modified multi-walled carbon nanotube with sodium 2-bromoethanesulfonate to obtain a modified multi-walled carbon nanotube; the preparation method comprises the following steps: reacting 1, 3, 5, 7-tetramethylcyclotetrasiloxane with 1, 3-bis (3-aminopropyl) tetramethyldisiloxane to obtain amino-terminated hydrogen-containing silicone oil; reacting hexamethylenediamine, double-end amino hydrogen-containing silicone oil and adipic acid to obtain modified polyamide; the modified polyamide and the modified multi-walled carbon nanotubes are subjected to ball milling and then subjected to electrostatic spinning, and spinning fibers are obtained; and reacting the spinning fiber with vinyl silicone oil, and spinning and weaving by using a spinning machine to prepare the self-cleaning antifouling fabric. The self-cleaning antifouling fabric prepared by the invention has excellent self-cleaning antifouling, antistatic, flame-retardant and mechanical properties.

Description

Technical Field

[0001] The invention relates to the field of textile fabrics, in particular to a self-cleaning and antifouling fabric and a preparation method thereof. Background Art

[0002] Nylon, also known as polyamide, is one of the earliest synthetic fibers to be industrialized. It has now become the second largest synthetic fiber for clothing after polyester. As clothing fabrics, nylon fibers have good mechanical properties, are light and soft, and are widely used in underwear, socks and other close-fitting fabrics, as well as functional fabrics such as mountaineering clothing and luggage fabrics. However, nylon has the obvious disadvantage of poor hydrophilicity. The main chain of the molecule lacks hydrophilic groups. Although there are relatively hydrophilic amide groups, they are blocked due to their high crystallinity. Therefore, nylon fabrics have poor hygroscopicity, are prone to static electricity and are not flame retardant, and their application and development are greatly limited. At the same time, clothing fabrics are easily contaminated by food, beverages, sweat, sebum, etc. during daily use. Therefore, the present invention prepares a self-cleaning and anti-fouling fabric with excellent antistatic and flame retardant properties. Summary of the invention

[0003] The purpose of the present invention is to provide a self-cleaning antifouling 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: The invention discloses a self-cleaning and antifouling fabric, which is obtained by electrostatic spinning after ball milling of modified polyamide and modified multi-walled carbon nanotubes, reacting with vinyl silicone oil, and finally spinning and weaving with a textile machine.

[0005] As an optimization, the vinyl silicone oil comes from Shandong Poly Chemical Co., Ltd.

[0006] As an optimization, the modified polyamide is obtained by reacting hexamethylenediamine, double-terminated amino-containing hydrogenated silicone oil and adipic acid.

[0007] As an optimization, the double-terminated amino hydrogen silicone oil is obtained by reacting 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane.

[0008] As an optimization, the modified multi-walled carbon nanotubes are obtained by reacting hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine and diethyl vinyl phosphate, and then reacting with sodium 2-bromoethylsulfonate.

[0009] As an optimization, the hydroxylated multi-walled carbon nanotube model is CNTs-006-2H, which comes from Suzhou Kaifa New Materials Technology Co., Ltd.

[0010] A method for preparing a self-cleaning antifouling fabric comprises the following preparation steps: (1) Mix hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine, zinc acetate and N,N-dimethylformamide in a mass ratio of 1:(2-3):(0.01-0.02):(8-10), stir at 20-30°C and 150-250 rpm for 20-30 min under a nitrogen atmosphere, add 4-5 times the mass of hydroxylated multi-walled carbon nanotubes of diethyl vinyl phosphate, heat to 140-150°C and stir for 25-35 min, heat to 195-205°C under vacuum and continue stirring for 55 min. ~65min, naturally cool to room temperature and then filter, wash with dichloromethane 3~5 times, dry at 60~70℃ for 10~12h to obtain pre-modified multi-walled carbon nanotubes; mix the pre-modified multi-walled carbon nanotubes, sodium 2-bromoethylsulfonate and deionized water in a mass ratio of 1:(3~5):(38~40), stir at 65~75℃ and 100~200rpm for 71~73h, cool to 35~45℃ and rotary evaporate for 30~40min, and dry at 55~65℃ for 4~6h to obtain modified multi-walled carbon nanotubes; (2) Mix 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane in a mass ratio of 1:(0.3~0.4), stir at 65~75°C and 100~200 rpm for 10~20 min, add trifluoromethylsulfonic acid (0.01~0.02 times the mass of 1,3,5,7-tetramethylcyclotetrasiloxane), continue stirring for 5~7 h, add anhydrous sodium carbonate to adjust the pH to 6~7, filter, and distill at 105~115°C and 0.1~0.3 MPa for 1~2 h to obtain a double-terminated amino hydrogenated silicone oil; (3) Mix hexamethylenediamine, double-terminated amino-containing hydrogen silicone oil and N,N-dimethylformamide in a molar ratio of 1:1:(4-5), stir at 55-65°C and 100-200 rpm for 20-30 min under a nitrogen environment, heat to 145-155°C, add adipic acid twice the molar amount of hexamethylenediamine, continue stirring for 2-4 h, cool naturally to room temperature, filter, wash with anhydrous ether 3-5 times, and dry at 60-70°C for 11-13 h to obtain a modified polyamide; (4) The modified polyamide and the modified multi-walled carbon nanotubes were mixed in a mass ratio of 1:(0.01-0.02), and the mixture was ball-milled for 2-4 h using a planetary ball mill with a quartz ball diameter of 5-7 mm and a ball milling speed of 50-150 rpm to obtain a composite powder; the composite powder, chloroplatinic acid and N,N-dimethylformamide were mixed in a mass ratio of 1:(0.01-0.02):(3-4), and the mixture was stirred at 20-30°C and 100-200 rpm for 10-20 min, and allowed to stand for 5-15 min to obtain a spinning solution; the spinning solution was subjected to a spinning voltage of 29 ~31kV, receiving distance 11~13cm, propulsion speed 0.01~0.03ml / min conditions for electrospinning, after completion, let it stand at 60~70℃ for 1~2h to obtain spun fibers; the spun fibers are soaked in vinyl silicone oil solution for 20~30min and then taken out, air-dried until no liquid drops within 5~15s, let it stand at 60~70℃ for 8~10h, washed with deionized water for 3~5 times, and dried at 55~65℃ for 11~13h to obtain self-cleaning and anti-fouling fibers; the self-cleaning and anti-fouling fibers are spun and woven by a textile machine to obtain self-cleaning and anti-fouling fabrics.

[0011] As an optimization, the reaction equation of the pre-modified multi-walled carbon nanotubes in step (1) is: .

[0012] As an optimization, the reaction equation for modifying the multi-walled carbon nanotubes in step (1) is: .

[0013] As an optimization, the reaction equation of the double-terminated amino-containing hydrogenated silicone oil in step (2) is: .

[0014] As an optimization, the reaction equation of the modified polyamide in step (3) is: .

[0015] As an optimization, the vinyl silicone oil solution in step (4) is obtained by mixing vinyl silicone oil, chloroplatinic acid and N,N-dimethylformamide in a mass ratio of 1:(0.01~0.02):(1~2).

[0016] Compared with the prior art, the beneficial effects achieved by the present invention are: When preparing the self-cleaning and antifouling fabric, the present invention comprises the following steps: reacting hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine and vinyl diethyl phosphate to obtain pre-modified multi-walled carbon nanotubes; reacting the pre-modified multi-walled carbon nanotubes and sodium 2-bromoethylsulfonate to obtain modified multi-walled carbon nanotubes; reacting 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane to obtain double-terminated amino-containing hydrogen silicone oil; reacting hexamethylenediamine, double-terminated amino-containing hydrogen silicone oil and adipic acid to obtain modified polyamide; ball-milling the modified polyamide and the modified multi-walled carbon nanotubes and then electrostatically spinning them to obtain spinning fibers; and reacting the spinning fibers and vinyl silicone oil to spin and weave them on a textile machine to prepare the self-cleaning and antifouling fabric.

[0017] Firstly, hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine and vinyl diethyl phosphate are reacted to obtain pre-modified multi-walled carbon nanotubes; then the pre-modified multi-walled carbon nanotubes are reacted with sodium 2-bromoethylsulfonate to obtain modified multi-walled carbon nanotubes; through the reaction of hydroxyl and chlorine, a polymer long chain containing phosphorus is generated on the surface of the hydroxylated multi-walled carbon nanotubes, which can react with hydrogen and free radicals in the combustion products, and can also generate a carbon film and isolate the outside air and heat, thereby improving the flame retardant properties of the self-cleaning and antifouling fabric; the tertiary amine on the polymer long chain can react with sodium 2-bromoethylsulfonate to generate zwitterions, which can combine with water molecules to form a hydration layer, hinder the adsorption of pollutants, and improve the self-cleaning and antifouling properties of the self-cleaning and antifouling fabric; at the same time, it can regulate the potential on the surface of the nanofiltration membrane to improve the antistatic properties of the self-cleaning and antifouling fabric.

[0018] Secondly, 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane are reacted to obtain double-terminal amino hydrogen-containing silicone oil; hexamethylenediamine, double-terminal amino hydrogen-containing silicone oil and adipic acid are reacted to obtain modified polyamide; the modified polyamide and modified multi-walled carbon nanotubes are ball-milled and then electrospun to obtain spinning fibers; the spinning fibers are reacted with vinyl silicone oil and then spun and woven on a textile machine to make self-cleaning and anti-fouling fabrics; by synthesizing double-terminal amino hydrogen-containing silicone oil to participate in the polymerization of the polyamide main chain, low surface energy hydrophobic silicon oxygen long chains are introduced, which can make pollutants and water It is difficult for molecules to adhere to the surface and can form a carbonized layer during combustion, preventing the contact of gas and oxygen, thereby enhancing the self-cleaning and anti-fouling properties and flame retardant properties of the self-cleaning and anti-fouling fabric. At the same time, the silicon-hydrogen bonds in the double-terminated amino hydrogen-containing silicone oil can react with the carbon-carbon double bonds on the modified multi-walled carbon nanotubes to form a cross-linked network, thereby improving the mechanical properties of the self-cleaning and anti-fouling fabric. Vinyl silicone oil is then used for impregnation, and an addition reaction is carried out with excess silicon-hydrogen bonds to increase the content of long silicon-oxygen chains and the formation of a cross-linked network structure, thereby further improving the self-cleaning and anti-fouling properties, flame retardant properties and mechanical properties of the self-cleaning and anti-fouling fabric. DETAILED DESCRIPTION

[0019] 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. Example 1

[0020] A method for preparing a self-cleaning antifouling fabric, the method comprising the following steps: (1) Mix hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine, zinc acetate and N,N-dimethylformamide in a mass ratio of 1:2:0.01:8, stir at 20°C and 150 rpm for 30 min under a nitrogen atmosphere, add vinyl diethyl phosphate (4 times the mass of hydroxylated multi-walled carbon nanotubes), heat to 140°C and stir for 35 min, heat to 195°C under vacuum and continue stirring for 65 min, cool naturally to room temperature and filter, wash with dichloromethane 3 times, and dry at 60°C for 12 h to obtain pre-modified multi-walled carbon nanotubes; mix pre-modified multi-walled carbon nanotubes, sodium 2-bromoethylsulfonate and deionized water in a mass ratio of 1:3:38, stir at 65°C and 100 rpm for 73 h, cool to 35°C and rotary evaporate for 40 min, and dry at 55°C for 6 h to obtain modified multi-walled carbon nanotubes; (2) 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane were mixed at a mass ratio of 1:0.3, stirred at 65°C and 100 rpm for 20 min, trifluoromethylsulfonic acid (0.01 times the mass of 1,3,5,7-tetramethylcyclotetrasiloxane) was added, and stirring was continued for 7 h. Anhydrous sodium carbonate was added to adjust the pH to 6, and then filtered. The mixture was distilled at 105°C and 0.1 MPa for 2 h to obtain a double-terminated amino hydrogenated silicone oil. (3) Hexamethylenediamine, double-terminated amino-containing hydrogenated silicone oil and N,N-dimethylformamide were mixed in a molar ratio of 1:1:4, stirred at 55°C and 100 rpm for 30 min under a nitrogen environment, heated to 145°C, and adipic acid was added in an amount twice the molar amount of hexamethylenediamine, and stirred for 4 h. After naturally cooling to room temperature, the mixture was filtered, washed with anhydrous ether for 3 times, and dried at 60°C for 13 h to obtain a modified polyamide; (4) The modified polyamide and the modified multi-walled carbon nanotubes were mixed in a mass ratio of 1:0.01, and ball milled for 4 h using a planetary ball mill with a quartz ball diameter of 5 mm and a ball milling speed of 50 rpm to obtain a composite powder; the composite powder, chloroplatinic acid and N,N-dimethylformamide were mixed in a mass ratio of 1:0.01:3, stirred at 20°C and 100 rpm for 20 min, and allowed to stand for 15 min to obtain a spinning solution; the spinning solution was subjected to a spinning voltage of 29 kV. V, receiving distance 11cm, propulsion speed 0.01ml / min conditions for electrospinning, after completion, let it stand at 60℃ for 2h to obtain spun fibers; the spun fibers were soaked in vinyl silicone oil solution for 20min and then taken out, aired until no liquid drops fell within 5s, let it stand at 60℃ for 10h, washed with deionized water 3 times, and dried at 55℃ for 13h to obtain self-cleaning and anti-fouling fibers; the self-cleaning and anti-fouling fibers were spun and woven by a textile machine to obtain self-cleaning and anti-fouling fabrics. Example 2

[0021] A method for preparing a self-cleaning antifouling fabric, the method comprising the following steps: (1) Mix hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine, zinc acetate and N,N-dimethylformamide in a mass ratio of 1:2.5:0.015:9, stir for 25 min at 25°C and 200 rpm under nitrogen atmosphere, add 4.5 times the mass of vinyl diethyl phosphate of hydroxylated multi-walled carbon nanotubes, heat to 145°C and stir for 30 min, heat to 200°C under vacuum and continue stirring for 60 min, cool naturally to room temperature and filter, wash with dichloromethane 4 times, and dry at 65°C for 11 h to obtain pre-modified multi-walled carbon nanotubes; mix pre-modified multi-walled carbon nanotubes, sodium 2-bromoethylsulfonate and deionized water in a mass ratio of 1:4:39, stir at 70°C and 150 rpm for 72 h, cool to 40°C and rotary evaporate for 35 min, and dry at 60°C for 5 h to obtain modified multi-walled carbon nanotubes; (2) 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane were mixed at a mass ratio of 1:0.35, stirred at 70°C and 150 rpm for 15 min, trifluoromethylsulfonic acid (0.015 times the mass of 1,3,5,7-tetramethylcyclotetrasiloxane) was added, stirring was continued for 6 h, anhydrous sodium carbonate was added to adjust the pH to 6.5, and then filtered, and distilled at 110°C and 0.2 MPa for 1.5 h to obtain a double-terminated amino hydrogenated silicone oil; (3) Hexamethylenediamine, double-terminated amino-containing hydrogenated silicone oil and N,N-dimethylformamide were mixed in a molar ratio of 1:1:4.5, stirred at 60°C and 150 rpm for 25 min under a nitrogen environment, heated to 150°C, and adipic acid was added in an amount twice the molar amount of hexamethylenediamine. The mixture was stirred for 3 h, cooled naturally to room temperature, filtered, washed with anhydrous ether 4 times, and dried at 65°C for 12 h to obtain a modified polyamide; (4) The modified polyamide and the modified multi-walled carbon nanotubes were mixed at a mass ratio of 1:0.015, and ball milled for 3 h using a planetary ball mill with a quartz ball diameter of 6 mm and a ball milling speed of 100 rpm to obtain a composite powder; the composite powder, chloroplatinic acid and N,N-dimethylformamide were mixed at a mass ratio of 1:0.015:3.5, stirred at 25°C and 150 rpm for 15 min, and allowed to stand for 10 min to obtain a spinning solution; the spinning solution was heated to 30 °C at a spinning voltage of 30 kV, receiving distance 12cm, propulsion speed 0.02ml / min, electrospinning was carried out, and after completion, it was allowed to stand at 65°C for 1.5h to obtain spun fibers; the spun fibers were soaked in vinyl silicone oil solution for 25min, taken out, and aired until no liquid droplets fell within 10s, allowed to stand at 65°C for 9h, washed with deionized water 4 times, and dried at 60°C for 12h to obtain self-cleaning and anti-fouling fibers; the self-cleaning and anti-fouling fibers were spun and woven by a textile machine to obtain self-cleaning and anti-fouling fabrics. Example 3

[0022] A method for preparing a self-cleaning antifouling fabric, the method comprising the following steps: (1) Mix hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine, zinc acetate and N,N-dimethylformamide in a mass ratio of 1:3:0.02:10, stir at 30°C and 250 rpm for 20 min under a nitrogen atmosphere, add vinyl diethyl phosphate (5 times the mass of hydroxylated multi-walled carbon nanotubes), heat to 150°C and stir for 25 min, heat to 205°C under vacuum and continue stirring for 55 min, cool naturally to room temperature and filter, wash with dichloromethane 5 times, and dry at 70°C for 10 h to obtain pre-modified multi-walled carbon nanotubes; mix pre-modified multi-walled carbon nanotubes, sodium 2-bromoethylsulfonate and deionized water in a mass ratio of 1:5:40, stir at 75°C and 200 rpm for 71 h, cool to 45°C and rotary evaporate for 30 min, and dry at 65°C for 4 h to obtain modified multi-walled carbon nanotubes; (2) 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane were mixed at a mass ratio of 1:0.4, stirred at 75°C and 200 rpm for 10 min, trifluoromethylsulfonic acid (0.02 times the mass of 1,3,5,7-tetramethylcyclotetrasiloxane) was added, and stirring was continued for 5 h. Anhydrous sodium carbonate was added to adjust the pH to 7, and then filtered. The mixture was distilled at 115°C and 0.3 MPa for 1 h to obtain a double-terminated amino hydrogenated silicone oil. (3) Hexamethylenediamine, double-terminated amino-containing hydrogenated silicone oil and N,N-dimethylformamide were mixed in a molar ratio of 1:1:5, stirred at 65°C and 200 rpm for 20 min under a nitrogen environment, heated to 155°C, and adipic acid was added in an amount twice the molar amount of hexamethylenediamine, and stirred for 2 h. After naturally cooling to room temperature, the mixture was filtered, washed with anhydrous ether for 5 times, and dried at 70°C for 11 h to obtain a modified polyamide; (4) The modified polyamide and the modified multi-walled carbon nanotubes were mixed in a mass ratio of 1:0.02, and the mixture was ball-milled for 2 h using a planetary ball mill with a quartz ball diameter of 7 mm and a ball milling speed of 150 rpm to obtain a composite powder; the composite powder, chloroplatinic acid and N,N-dimethylformamide were mixed in a mass ratio of 1:0.02:4, stirred at 30 °C and 200 rpm for 10 min, and allowed to stand for 5 min to obtain a spinning solution; the spinning solution was subjected to a spinning voltage of 31 kV. Electrospinning was carried out under the conditions of V, receiving distance of 13 cm, and propulsion speed of 0.03 ml / min. After completion, it was allowed to stand at 70°C for 1 hour to obtain spun fibers; the spun fibers were soaked in a vinyl silicone oil solution for 30 minutes and then taken out, dried until no liquid droplets fell within 15 seconds, allowed to stand at 70°C for 8 hours, washed with deionized water for 5 times, and dried at 65°C for 11 hours to obtain self-cleaning and anti-fouling fibers; the self-cleaning and anti-fouling fibers were spun and woven by a textile machine to obtain self-cleaning and anti-fouling fabrics.

[0023] Comparative Example 1 A method for preparing a self-cleaning antifouling fabric, the method comprising the following steps: (1) Mix hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine, zinc acetate and N,N-dimethylformamide in a mass ratio of 1:2.5:0.015:9, stir at 200 rpm at 25°C for 25 min under a nitrogen atmosphere, add 4.5 times the mass of hydroxylated multi-walled carbon nanotubes of diethyl vinyl phosphate, heat to 145°C and stir for 30 min, heat to 200°C under vacuum and continue stirring for 60 min, cool naturally to room temperature and filter, wash with dichloromethane 4 times, and dry at 65°C for 11 h to obtain modified multi-walled carbon nanotubes; (2) 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane were mixed at a mass ratio of 1:0.35, stirred at 70°C and 150 rpm for 15 min, trifluoromethylsulfonic acid (0.015 times the mass of 1,3,5,7-tetramethylcyclotetrasiloxane) was added, stirring was continued for 6 h, anhydrous sodium carbonate was added to adjust the pH to 6.5, and then filtered, and distilled at 110°C and 0.2 MPa for 1.5 h to obtain a double-terminated amino hydrogenated silicone oil; (3) Hexamethylenediamine, double-terminated amino-containing hydrogenated silicone oil and N,N-dimethylformamide were mixed in a molar ratio of 1:1:4.5, stirred at 60°C and 150 rpm for 25 min under a nitrogen environment, heated to 150°C, and adipic acid was added in an amount twice the molar amount of hexamethylenediamine. The mixture was stirred for 3 h, cooled naturally to room temperature, filtered, washed with anhydrous ether 4 times, and dried at 65°C for 12 h to obtain a modified polyamide; (4) The modified polyamide and the modified multi-walled carbon nanotubes were mixed at a mass ratio of 1:0.015, and ball milled for 3 h using a planetary ball mill with a quartz ball diameter of 6 mm and a ball milling speed of 100 rpm to obtain a composite powder; the composite powder, chloroplatinic acid and N,N-dimethylformamide were mixed at a mass ratio of 1:0.015:3.5, stirred at 25°C and 150 rpm for 15 min, and allowed to stand for 10 min to obtain a spinning solution; the spinning solution was heated to 30 °C at a spinning voltage of 30 kV, receiving distance 12cm, propulsion speed 0.02ml / min, electrospinning was carried out, and after completion, it was allowed to stand at 65°C for 1.5h to obtain spun fibers; the spun fibers were soaked in vinyl silicone oil solution for 25min, taken out, and aired until no liquid droplets fell within 10s, allowed to stand at 65°C for 9h, washed with deionized water 4 times, and dried at 60°C for 12h to obtain self-cleaning and anti-fouling fibers; the self-cleaning and anti-fouling fibers were spun and woven by a textile machine to obtain self-cleaning and anti-fouling fabrics.

[0024] Comparative Example 2 A method for preparing a self-cleaning antifouling fabric, the method comprising the following steps: (1) 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane were mixed at a mass ratio of 1:0.35, stirred at 70°C and 150 rpm for 15 min, trifluoromethylsulfonic acid (0.015 times the mass of 1,3,5,7-tetramethylcyclotetrasiloxane) was added, and stirring was continued for 6 h. Anhydrous sodium carbonate was added to adjust the pH to 6.5, and then filtered. The mixture was distilled at 110°C and 0.2 MPa for 1.5 h to obtain a double-terminated amino-containing hydrogenated silicone oil. (2) Hexamethylenediamine, double-terminated amino-containing hydrogenated silicone oil and N,N-dimethylformamide were mixed in a molar ratio of 1:1:4.5, stirred at 60°C and 150 rpm for 25 min under a nitrogen environment, heated to 150°C, and adipic acid was added in an amount twice the molar amount of hexamethylenediamine, and stirred for 3 h. After naturally cooling to room temperature, the mixture was filtered, washed with anhydrous ether for 4 times, and dried at 65°C for 12 h to obtain a modified polyamide; (3) The modified polyamide and multi-walled carbon nanotubes were mixed in a mass ratio of 1:0.015, and ball milled for 3 h using a planetary ball mill with a quartz ball diameter of 6 mm and a ball milling speed of 100 rpm to obtain a composite powder; the composite powder, chloroplatinic acid and N,N-dimethylformamide were mixed in a mass ratio of 1:0.015:3.5, stirred at 25 °C and 150 rpm for 15 min, and allowed to stand for 10 min to obtain a spinning solution; the spinning solution was heated to 30 kV at a spinning voltage of 30 kV. V, receiving distance 12cm, propulsion speed 0.02ml / min conditions for electrospinning, after completion, let it stand at 65℃ for 1.5h to obtain spun fibers; the spun fibers were soaked in vinyl silicone oil solution for 25min and then taken out, aired until no liquid droplets fell within 10s, let it stand at 65℃ for 9h, washed with deionized water 4 times, and dried at 60℃ for 12h to obtain self-cleaning and anti-fouling fibers; the self-cleaning and anti-fouling fibers were spun and woven by a textile machine to obtain self-cleaning and anti-fouling fabrics.

[0025] Comparative Example 3 A method for preparing a self-cleaning antifouling fabric, the method comprising the following steps: (1) Mix hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine, zinc acetate and N,N-dimethylformamide in a mass ratio of 1:2.5:0.015:9, stir for 25 min at 25°C and 200 rpm under nitrogen atmosphere, add 4.5 times the mass of vinyl diethyl phosphate of hydroxylated multi-walled carbon nanotubes, heat to 145°C and stir for 30 min, heat to 200°C under vacuum and continue stirring for 60 min, cool naturally to room temperature and filter, wash with dichloromethane 4 times, and dry at 65°C for 11 h to obtain pre-modified multi-walled carbon nanotubes; mix pre-modified multi-walled carbon nanotubes, sodium 2-bromoethylsulfonate and deionized water in a mass ratio of 1:4:39, stir at 70°C and 150 rpm for 72 h, cool to 40°C and rotary evaporate for 35 min, and dry at 60°C for 5 h to obtain modified multi-walled carbon nanotubes; (2) Hexamethylenediamine and N,N-dimethylformamide were mixed at a molar ratio of 1:4.5, stirred at 60°C and 150 rpm for 25 min under a nitrogen environment, heated to 150°C, and adipic acid was added in an amount 1 times the molar amount of hexamethylenediamine, and stirred for 3 h. After naturally cooling to room temperature, the mixture was filtered, washed with anhydrous ether for 4 times, and dried at 65°C for 12 h to obtain polyamide; (3) Polyamide and modified multi-walled carbon nanotubes were mixed in a mass ratio of 1:0.015, and ball-milled for 3 h using a planetary ball mill with a quartz ball diameter of 6 mm and a ball milling speed of 100 rpm to obtain a composite powder; the composite powder and N,N-dimethylformamide were mixed in a mass ratio of 1:3.5, stirred at 25°C and 150 rpm for 15 min, and allowed to stand for 10 min to obtain a spinning solution; the spinning solution was electrospun under the conditions of a spinning voltage of 30 kV, a receiving distance of 12 cm, and a propulsion speed of 0.02 ml / min, and then allowed to stand at 65°C for 1.5 h to obtain spun fibers; the spun fibers were soaked in a vinyl silicone oil solution for 25 min, taken out, and aired until no liquid drops fell within 10 s, allowed to stand at 65°C for 9 h, washed with deionized water 4 times, and dried at 60°C for 12 h to obtain self-cleaning and anti-fouling fibers; the self-cleaning and anti-fouling fibers were spun and woven by a textile machine to obtain self-cleaning and anti-fouling fabrics.

[0026] Comparative Example 4 A method for preparing a self-cleaning antifouling fabric, the method comprising the following steps: (1) Mix hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine, zinc acetate and N,N-dimethylformamide in a mass ratio of 1:2.5:0.015:9, stir for 25 min at 25°C and 200 rpm under nitrogen atmosphere, add 4.5 times the mass of vinyl diethyl phosphate of hydroxylated multi-walled carbon nanotubes, heat to 145°C and stir for 30 min, heat to 200°C under vacuum and continue stirring for 60 min, cool naturally to room temperature and filter, wash with dichloromethane 4 times, and dry at 65°C for 11 h to obtain pre-modified multi-walled carbon nanotubes; mix pre-modified multi-walled carbon nanotubes, sodium 2-bromoethylsulfonate and deionized water in a mass ratio of 1:4:39, stir at 70°C and 150 rpm for 72 h, cool to 40°C and rotary evaporate for 35 min, and dry at 60°C for 5 h to obtain modified multi-walled carbon nanotubes; (2) 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane were mixed at a mass ratio of 1:0.35, stirred at 70°C and 150 rpm for 15 min, trifluoromethylsulfonic acid (0.015 times the mass of 1,3,5,7-tetramethylcyclotetrasiloxane) was added, stirring was continued for 6 h, anhydrous sodium carbonate was added to adjust the pH to 6.5, and then filtered, and distilled at 110°C and 0.2 MPa for 1.5 h to obtain a double-terminated amino hydrogenated silicone oil; (3) Hexamethylenediamine, double-terminated amino-containing hydrogenated silicone oil and N,N-dimethylformamide were mixed in a molar ratio of 1:1:4.5, stirred at 60°C and 150 rpm for 25 min under a nitrogen environment, heated to 150°C, and adipic acid was added in an amount twice the molar amount of hexamethylenediamine. The mixture was stirred for 3 h, cooled naturally to room temperature, filtered, washed with anhydrous ether 4 times, and dried at 65°C for 12 h to obtain a modified polyamide; (4) The modified polyamide and the modified multi-walled carbon nanotubes were mixed in a mass ratio of 1:0.015, and the mixture was ball-milled for 3 h using a planetary ball mill at a quartz ball diameter of 6 mm and a ball milling speed of 100 rpm to obtain a composite powder; the composite powder, chloroplatinic acid and N,N-dimethylformamide were mixed in a mass ratio of 1:0.015:3.5, stirred at 25 °C and 150 rpm for 15 min, and allowed to stand for 10 min to obtain a spinning solution; the spinning solution was electrospun at a spinning voltage of 30 kV, a receiving distance of 12 cm, and a propulsion speed of 0.02 ml / min, and then allowed to stand at 65 °C for 9 h, washed with deionized water 4 times, and dried at 60 °C for 12 h to obtain a self-cleaning anti-fouling fiber; the self-cleaning anti-fouling fiber was spun and woven on a textile machine to obtain a self-cleaning anti-fouling fabric.

[0027] Test Case 1. Self-cleaning and anti-fouling performance Test method: Take samples of 100mm×100mm size from the self-cleaning and antifouling fabrics obtained in each embodiment and the comparative example respectively, and drop a drop of 10μL of soy sauce at three positions from the top at an interval of 50mm according to GB / T30159. Cover and wipe with absorbent paper after 30s, and rate the samples according to the surface conditions to judge the self-cleaning and antifouling performance.

[0028] 2. Antistatic properties Test method: Take 200mm×25mm of the self-cleaning and antifouling fabrics obtained in each embodiment and the comparative example respectively, and use RST-400 friction voltage tester to test the friction voltage in accordance with GB / T12703.

[0029] 3. Flame retardant properties Test method: The self-cleaning and antifouling fabrics obtained in each embodiment and the comparative example were taken in a size of 100mm×10mm, and the limiting oxygen index was tested according to GB / T2406 to determine the flame retardant performance.

[0030] 4. Mechanical properties Test method: Take 10 mm of the self-cleaning and antifouling fiber obtained in each embodiment and the control example respectively, use LLY-06 electronic single fiber strength tester, at a tensile speed of 10 mm / min, to test the breaking strength and judge the mechanical properties.

[0031] Table 1 below shows the analysis results of the self-cleaning and antifouling properties, antistatic properties, flame retardant properties and mechanical properties of the self-cleaning and antifouling fabrics of Examples 1 to 3 of the present invention and Comparative Examples 1 to 4.

[0032] Table 1

[0033] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 1, it can be found that the self-cleaning and antifouling fabric prepared by the present invention has good self-cleaning and antifouling performance, antistatic performance, flame retardant performance and mechanical properties.

[0034] By comparison, Examples 1, 2, and 3 have higher contamination levels and lower friction charging voltages than Comparative Example 1, indicating that the tertiary amine on the polymer long chain can react with sodium 2-bromoethylsulfonate to form zwitterions, which can combine with water molecules to form a hydration layer, hinder the adsorption of pollutants, and improve the self-cleaning and anti-fouling properties of the self-cleaning and anti-fouling fabric; at the same time, it can regulate the electric potential on the surface of the nanofiltration membrane and improve the antistatic properties of the self-cleaning and anti-fouling fabric.

[0035] By comparison, the limiting oxygen index and breaking strength of Examples 1, 2, and 3 are higher than those of Comparative Example 2, indicating that a polymer long chain containing phosphorus is generated on the surface of the hydroxylated multi-walled carbon nanotubes through the reaction of hydroxyl and chlorine, which can react with hydrogen and free radicals in the combustion products to generate a carbon film and isolate external air and heat, thereby improving the flame retardant properties of the self-cleaning and antifouling fabric; at the same time, the carbon-carbon double bonds on the modified multi-walled carbon nanotubes can undergo an addition reaction with the silicon-hydrogen bonds on the modified polyamide main chain to form a cross-linked network, thereby improving the mechanical properties of the self-cleaning and antifouling fabric.

[0036] By comparison, the contamination level, limiting oxygen index and breaking strength of Examples 1, 2 and 3 are higher than that of Comparative Example 3, which shows that by synthesizing the double-terminal amino hydrogen-containing silicone oil to participate in the polymerization of the polyamide main chain and introducing low surface energy hydrophobic silicon oxygen long chains, it is possible to make it difficult for pollutants and water molecules to adhere to the surface, and it can also form a carbonized layer during combustion to prevent the contact between gas and oxygen, thereby enhancing the self-cleaning and anti-fouling properties and flame retardant properties of the self-cleaning and anti-fouling fabric; at the same time, the silicon-hydrogen bonds in the double-terminal amino hydrogen-containing silicone oil can undergo addition reaction with the carbon-carbon double bonds on the modified multi-walled carbon nanotubes to form a cross-linked network, thereby improving the mechanical properties of the self-cleaning and anti-fouling fabric.

[0037] By comparison, Examples 1, 2, and 3 have higher stain levels, limiting oxygen indexes, and breaking strengths than Example 4, indicating that the use of vinyl silicone oil impregnation and the addition reaction of excess silicon-hydrogen bonds can increase the content of long silicon-oxygen chains and the formation of a cross-linked network structure, thereby further improving the self-cleaning and anti-fouling properties, flame retardant properties, and mechanical properties of the self-cleaning and anti-fouling fabric.

[0038] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A self-cleaning and anti-fouling fabric, characterized in that: The self-cleaning and antifouling fabric is obtained by electrostatic spinning after ball milling of modified polyamide and modified multi-walled carbon nanotubes, reacting with vinyl silicone oil, and finally spinning and weaving with a textile machine.

2. A self-cleaning antifouling fabric according to claim 1, characterized in that: The modified polyamide is obtained by reacting hexamethylenediamine, double-terminated amino-containing hydrogenated silicone oil and adipic acid.

3. A self-cleaning antifouling fabric according to claim 2, characterized in that: The double-terminated amino hydrogen-containing silicone oil is obtained by reacting 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane.

4. The self-cleaning antifouling fabric according to claim 1, characterized in that: The modified multi-walled carbon nanotubes are obtained by reacting hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine and diethyl vinyl phosphate, and then reacting with sodium 2-bromoethylsulfonate.

5. A method for preparing a self-cleaning antifouling fabric, characterized in that: The method comprises the following preparation steps: (1) Mix hydroxylated multi-walled carbon nanotubes, N-methyldiethanolamine, zinc acetate and N,N-dimethylformamide in a mass ratio of 1:(2-3):(0.01-0.02):(8-10), stir at 20-30°C and 150-250 rpm for 20-30 min under a nitrogen atmosphere, add 4-5 times the mass of hydroxylated multi-walled carbon nanotubes of diethyl vinyl phosphate, heat to 140-150°C and stir for 25-35 min, heat to 195-205°C under vacuum and continue stirring for 55 min. ~65min, naturally cool to room temperature and then filter, wash with dichloromethane 3~5 times, dry at 60~70℃ for 10~12h to obtain pre-modified multi-walled carbon nanotubes; mix the pre-modified multi-walled carbon nanotubes, sodium 2-bromoethylsulfonate and deionized water in a mass ratio of 1:(3~5):(38~40), stir at 65~75℃ and 100~200rpm for 71~73h, cool to 35~45℃ and rotary evaporate for 30~40min, and dry at 55~65℃ for 4~6h to obtain modified multi-walled carbon nanotubes; (2) Mix 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane in a mass ratio of 1:(0.3~0.4), stir at 65~75°C and 100~200 rpm for 10~20 min, add trifluoromethylsulfonic acid (0.01~0.02 times the mass of 1,3,5,7-tetramethylcyclotetrasiloxane), continue stirring for 5~7 h, add anhydrous sodium carbonate to adjust the pH to 6~7, filter, and distill at 105~115°C and 0.1~0.3 MPa for 1~2 h to obtain a double-terminated amino hydrogenated silicone oil; (3) Mix hexamethylenediamine, double-terminated amino-containing hydrogen silicone oil and N,N-dimethylformamide in a molar ratio of 1:1:(4-5), stir at 55-65°C and 100-200 rpm for 20-30 min under a nitrogen environment, heat to 145-155°C, add adipic acid twice the molar amount of hexamethylenediamine, continue stirring for 2-4 h, cool naturally to room temperature, filter, wash with anhydrous ether 3-5 times, and dry at 60-70°C for 11-13 h to obtain a modified polyamide; (4) The modified polyamide and the modified multi-walled carbon nanotubes were mixed in a mass ratio of 1:(0.01-0.02), and the mixture was ball-milled for 2-4 h using a planetary ball mill with a quartz ball diameter of 5-7 mm and a ball milling speed of 50-150 rpm to obtain a composite powder; the composite powder, chloroplatinic acid and N,N-dimethylformamide were mixed in a mass ratio of 1:(0.01-0.02):(3-4), and the mixture was stirred at 20-30°C and 100-200 rpm for 10-20 min, and allowed to stand for 5-15 min to obtain a spinning solution; the spinning solution was subjected to a spinning voltage of 29 ~31kV, receiving distance 11~13cm, propulsion speed 0.01~0.03ml / min conditions for electrospinning, after completion, let it stand at 60~70℃ for 1~2h to obtain spun fibers; the spun fibers are soaked in vinyl silicone oil solution for 20~30min and then taken out, air-dried until no liquid drops within 5~15s, let it stand at 60~70℃ for 8~10h, washed with deionized water for 3~5 times, and dried at 55~65℃ for 11~13h to obtain self-cleaning and anti-fouling fibers; the self-cleaning and anti-fouling fibers are spun and woven by a textile machine to obtain self-cleaning and anti-fouling fabrics.

6. The method for preparing a self-cleaning antifouling fabric according to claim 5, characterized in that: The reaction equation for the pre-modified multi-walled carbon nanotubes in step (1) is: 。 7. The method for preparing a self-cleaning antifouling fabric according to claim 5, characterized in that: The reaction equation for modifying multi-walled carbon nanotubes in step (1) is: 。 8. The method for preparing a self-cleaning antifouling fabric according to claim 5, characterized in that: The reaction equation of the double-terminated amino-containing hydrogen silicone oil in step (2) is: 。 9. The method for preparing a self-cleaning antifouling fabric according to claim 5, characterized in that: The reaction equation of the modified polyamide in step (3) is: 。 10. The method for preparing a self-cleaning antifouling fabric according to claim 5, characterized in that: The vinyl silicone oil solution in step (4) is obtained by mixing vinyl silicone oil, chloroplatinic acid and N,N-dimethylformamide in a mass ratio of 1:(0.01-0.02):(1-2).

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