Antibacterial functional clothing fabric and preparation method thereof

Abstract

The application discloses an antibacterial functional clothing fabric and a preparation method thereof, and relates to the field of functional fabrics. The antibacterial functional clothing fabric prepared by the application is obtained by impregnating a fiber fabric with a finishing agent; the fiber fabric is obtained by spinning modified polyamide fibers; the modified polyamide fibers are obtained by spinning modified polyamide; and the fiber fabric is obtained by impregnating the fiber fabric with the finishing agent. The modified polyamide fibers are obtained by spinning modified polyamide. The antibacterial functional clothing fabric not only improves the mechanical strength of the fibers, but also has antibacterial function. The finishing agent is obtained by the reaction of epoxy allyl siloxane and carboxyl polyoxyethylene ether. The epoxy allyl siloxane is obtained by the reaction of 1,3-bis(chloromethyl)tetramethyldisiloxane and o-allyl phenol and then oxidation. The carboxyl polyoxyethylene ether is obtained by the reaction of propanetricarboxylic acid and methyl allyl alcohol polyoxyethylene ether. The fabric has both hydrophilic and antistatic properties, and the wear resistance of the fabric is enhanced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of functional fabric, in particular to an antibacterial functional clothing fabric and a preparation method thereof. BACKGROUND

[0002] The popular clothing fabric on the market is divided into two categories: natural and synthetic. Natural ones are made of natural fibers such as silk, pure cotton, and hemp. Synthetic clothing fabrics include various chemical fibers, such as chemical fibers, acrylic, polypropylene, nylon filaments, and short filaments. Semi-synthetic fibers such as acetate fibers and copper ammonia fibers are also included. In addition, there are blended fabrics of chemical fibers and natural fibers.

[0003] Polyamide fiber (commonly known as nylon or chinlon) is a synthetic polymer fiber with amide bond as the repeating structural unit. It has excellent performance, but low moisture absorption and often relies on finishing for antibacterial properties. Therefore, the present application studies and prepares an antibacterial functional clothing fabric that is both hydrophilic and antibacterial. SUMMARY

[0004] The technical problem to be solved by the present application is to provide an antibacterial functional clothing fabric with mechanical strength and antibacterial function and a preparation method thereof.

[0005] A technical solution proposed by the present application to solve the above technical problem is: an antibacterial functional clothing fabric is prepared by impregnating a fiber fabric with a finishing agent; the fiber fabric is prepared by spinning modified polyamide fibers; the modified polyamide fibers are prepared by spinning modified polyamide; the finishing agent is prepared by reacting epoxy allyl siloxane with carboxyl polyoxyethylene ether.

[0006] Preferably, the modified polyamide is prepared by melting polyamide, modified polyethylene glycol, and epoxy itaconic acid-based unsaturated polyester; the modified polyethylene glycol is prepared by reacting polyethylene glycol, 3-mercaptopropionic acid, and epichlorohydrin.

[0007] Preferably, the epoxy itaconic acid-based unsaturated polyester is prepared by reacting itaconic acid-based unsaturated polyester with propylene aldehyde, and then reacting with mercapto isocyanate; the mercapto isocyanate is prepared by reacting bis(3-mercaptopropionic acid) ethylene glycol with isocyanate.

[0008] Preferably, the epoxy allyl siloxane is prepared by reacting 1,3-bis(chloromethyl) tetramethyl disiloxane with o-allyl phenol and then oxidizing; the carboxyl polyoxyethylene ether is prepared by reacting tricarballylic acid with methyl allyl alcohol polyoxyethylene ether.

[0009] Preferably, the preparation method of the antibacterial functional clothing fabric comprises the following specific steps:

[0010] Preferably, the preparation method of the antibacterial functional clothing fabric comprises the following specific steps:S1. Under the atmosphere of nitrogen, the itaconic acid-based unsaturated polyester is mixed with acetone at a mass ratio of 1:2-3, heated to 60-70℃, stirred uniformly, then 0.001-0.003 times the mass of the itaconic acid-based unsaturated polyester of the polymerization inhibitor hydroquinone is added, 0.2-0.3 times the mass of the itaconic acid-based unsaturated polyester of acrolein is added dropwise at a rate of 1-3 ml / min, 0.002-0.004 times the mass of the itaconic acid-based unsaturated polyester of the catalyst triethylamine is added, heated to 80-90℃, reacted for 6-8 h, distilled under reduced pressure, precipitated with diethyl ether, then the mercaptoisocyanate, the photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and tetrahydrofuran are added, the mass ratio of the itaconic acid-based unsaturated polyester, the mercaptoisocyanate, the photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and tetrahydrofuran is 40:12-13:0.12:0.12, irradiated with a 365 nm UV lamp at 10 mW / cm² for 30-50 min, dialyzed, with a molecular weight cutoff of 1000 Da, and finally freeze-dried at -40--60℃ to obtain the epoxy itaconic acid-based unsaturated polyester;

[0011] S2. The polyamide, the modified polyethylene glycol, the epoxy itaconic acid-based unsaturated polyester and the compatible agent maleic anhydride grafted polyethylene are mixed at a mass ratio of 70:18:9-13:2 and placed in a twin-screw extruder, melt-extruded and granulated, the temperature of the feeding section is 240-242℃, the temperature of the melting section is 250-252℃, the temperature of the mixing section is 260-262℃, the temperature of the die head is 255-257℃, the screw rotation speed is 120-150 rpm, the residence time is 3-5 min, then the granules are placed in a melt spinning machine to be melt-spun after being water-cooled and cut, the spinning temperature is 265-268℃, to obtain the modified polyamide fiber, which is woven into a garment fabric;

[0012] S3. The allyl siloxane, formic acid, toluene and concentrated sulfuric acid are mixed at a mass ratio of 40-60:100:10:1-2, stirred uniformly, then 0.1-0.3 times the mass of the allyl siloxane of a 30% mass fraction hydrogen peroxide solution is added dropwise at a rate of 1-3 ml / min, heated to 60-63℃, reacted for 6-7 h, quenched with ice water, washed with saturated sodium bicarbonate solution for 3-5 times, dried with anhydrous sodium sulfate, distilled under reduced pressure, to obtain the epoxy allyl siloxane;

[0013] S4. Under the atmosphere of nitrogen, the carboxyl polyoxyethylene ether is mixed with acetone at a mass ratio of 1:4-6, heated to 60-70℃, stirred and dissolved, then 0.02-0.03 times the mass of the carboxyl polyoxyethylene ether of the catalyst triethylamine is added, stirred uniformly, then 1.1-1.2 times the mass of the carboxyl polyoxyethylene ether of the epoxy allyl siloxane is added, heated to 80-90℃, reacted for 6-8 h, the pH is adjusted to 6.8-7.2 with hydrochloric acid, to obtain the finishing agent;

[0014] S5. The garment fabric is immersed in the finishing agent with a bath ratio of 1:10~12, heated to 80~90℃, immersed for 30~50min, and then dried at 110~130℃ to obtain the antibacterial functional garment fabric.

[0015] Preferably, in step S1, the itaconic acid-based unsaturated polyester is prepared by mixing 1,4-succinic acid, itaconic acid and 1,4-butanediol in a molar ratio of 3:7:10~11 under a nitrogen atmosphere, stirring uniformly, adding a catalyst tetrabutyl titanate in an amount of 0.01~0.03 times the mass of itaconic acid, adding a polymerization inhibitor hydroquinone in an amount of 0.02~0.03 times the mass of itaconic acid, heating to 170~172℃, stirring at 800~1200rpm for 6~8h, heating to 180~182℃, esterifying at 0.09~0.095MPa for 3~4h to obtain the itaconic acid-based unsaturated polyester.

[0016] Preferably, in step S1, the mercapto isocyanate is prepared by mixing triethylamine, bis(3-mercaptopropionic acid) ethylene glycol and acetone in a mass ratio of 0.22~0.32:22~32:20~40, uniformly dispersing, adding isocyanate in an amount of 0.6~0.8 times the molar mass of bis(3-mercaptopropionic acid) ethylene glycol, stirring at 800~1200rpm at room temperature for 12~15h, distilling under reduced pressure and precipitating with ethyl ether, suction filtering, washing with ethyl ether for 3~5 times, and vacuum drying at 25~35℃ to obtain the mercapto isocyanate.

[0017] Preferably, in step S2, the modified polyethylene glycol is prepared by mixing polyethylene glycol, benzyltriethylammonium chloride and a sodium hydroxide solution with a mass fraction of 10~30% in a mass ratio of 100:0.05~0.5:8~10, heating to 45~55℃, uniformly stirring, adding epichlorohydrin in an amount of 0.2~0.22 times the mass of polyethylene glycol at a rate of 1~3ml / min, reacting for 3~4h, distilling under reduced pressure and adjusting the pH to 6.8~7.2 with hydrochloric acid, filtering, adding acetone, 3-mercaptopropionic acid and a catalyst triethylamine in a mass ratio of 100:20~30:12~15:0.2~0.4, stirring at 200~400rpm at room temperature for 18~24h, terminating the reaction with ice water, extracting with ethyl ether, and distilling under reduced pressure to obtain the modified polyethylene glycol.

[0018] Preferably, in step S3 above, the preparation method of allylsiloxane is as follows: under a nitrogen atmosphere, o-allylphenol and dimethylformamide are mixed at a mass ratio of 1:5~6, heated to 60~70℃, potassium hydroxide catalyst (0.018~0.022 times the mass of o-allylphenol) and tetrabutylammonium bromide catalyst (0.012~0.014 times the mass of o-allylphenol) are added, stirred evenly, and 1,3-bis(chloromethyl)tetramethyldisiloxane (0.71~0.73 times the mass of o-allylphenol) is added dropwise at a rate of 1~3 ml / min, heated to 80~82℃, refluxed for 8~16 h, cooled to room temperature, pH adjusted to 6.8~7.2 with hydrochloric acid, filtered and distilled under reduced pressure, extracted with diethyl ether, dried with anhydrous sodium sulfate, and rotary evaporated to obtain allylsiloxane.

[0019] Preferably, in step S4 above, the preparation method of carboxylated polyoxyethylene ether is as follows: under a nitrogen atmosphere, malonic acid, methyl allyl alcohol polyoxyethylene ether and acetone are mixed in a mass ratio of 3:7~8:10, heated to 60~80℃, stirred evenly, and then 0.01~0.02 times the mass of malonic acid catalyst p-toluenesulfonic acid is added. The mixture is kept at 200~300 rpm for 4~6 hours, the pH is adjusted to 6~7 with a 10% sodium hydroxide solution, the mixture is distilled under reduced pressure, and then washed with diethyl ether 3~5 times to obtain carboxylated polyoxyethylene ether.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0021] The antibacterial functional clothing fabric prepared by this invention is obtained by impregnating fiber fabric with a finishing agent; the fiber fabric is spun from modified polyamide fiber, and the modified polyamide fiber is spun from modified polyamide.

[0022] Modified polyamide is obtained by melt spinning polyamide, modified polyethylene glycol, and epoxy itaconic acid-based unsaturated polyester. Modified polyethylene glycol is obtained by reacting polyethylene glycol, 3-mercaptopropionic acid, and epichlorohydrin. Epoxy itaconic acid-based unsaturated polyester is obtained by reacting itaconic acid-based unsaturated polyester with acrolein, followed by reaction with mercapto isocyanate. Mercapto isocyanate is obtained by reacting bis(3-mercaptopropionic acid) ethylene glycol with isocyanate. Modified polyamide fibers, obtained by melt spinning polyamide, modified polyvinyl alcohol, and epoxy itaconic acid-based unsaturated polyester, exhibit intermolecular interactions, forming a complex cross-linked structure. This not only improves the mechanical strength of the fiber but also provides antibacterial properties. The hydroxyl and mercapto groups on the modified polyamide fibers can also react with finishing agents, allowing the finishing agents to bind tightly to the fiber molecules and enhancing adhesion.

[0023] The finishing agent is prepared by reacting epoxy allyl siloxane with carboxyl polyoxyethylene ether, the epoxy allyl siloxane is prepared by reacting 1,3-bis(chloromethyl)tetramethyldisiloxane with o-allyl phenol and then oxidizing, and the carboxyl polyoxyethylene ether is prepared by reacting tricarballylic acid with methyl allyl alcohol polyoxyethylene ether; the epoxy allyl siloxane is ring-opening reacted with the carboxyl polyoxyethylene ether with carboxyl to form a siloxane finishing agent with polyoxyethylene ether, which improves the hydrophilicity and enables the fabric to have both hydrophilicity and antistatic property; and the fabric finished by the finishing agent also forms a dense protective film on the surface, thereby enhancing the wear resistance of the fabric. DETAILED DESCRIPTION

[0024] The present application will be described in detail below through examples, and it is necessary to point out here that the following examples are only used to further illustrate the present application and cannot be understood as limiting the protection scope of the present application, and those skilled in the art can make some non-essential improvements and adjustments to the present application according to the above content of the present application. Unless otherwise defined, all professional and scientific terms used herein have the same meaning as familiar to those skilled in the art.

[0025] In order to more clearly illustrate the method provided by the present application, the following examples are used to illustrate in detail, and the test methods of various indexes of the antibacterial functional fabric prepared in the examples and comparative examples are as follows:

[0026] Mechanical property: the antibacterial functional fabric prepared in the examples and comparative examples is tested for elongation at break according to GB / T 14337.

[0027] Antibacterial property: the antibacterial functional fabric prepared in the examples and comparative examples is tested for inhibition rate according to GB / T 20944.1.

[0028] Hydrophilicity: the antibacterial functional fabric prepared in the examples and comparative examples is tested for wicking height according to FZ / T 50040.

[0029] Antistatic property: the antibacterial functional fabric prepared in the examples and comparative examples is tested for resistivity according to GB / T 12014.

[0030] Adhesion: the antibacterial functional fabric prepared in the examples and comparative examples is tested for hydrophilicity again after soaping for 50 times.

[0031] Wear resistance: the antibacterial functional fabric prepared in the examples and comparative examples is tested for wear resistance according to GB / T 21196, with 5000 times as the interval number of rubbing, and the number of rubbing before wear is recorded.

[0032] Example 1

[0033] The preparation method of the antibacterial functional fabric in the present example is:

[0034] S1. Under a nitrogen atmosphere, 1,4-succinic acid, itaconic acid and 1,4-butanediol were mixed in a molar ratio of 3:7:10, stirred uniformly, 0.01 times the mass of itaconic acid of catalyst tetrabutyl titanate and 0.02 times the mass of itaconic acid of polymerization inhibitor hydroquinone were added, the temperature was raised to 170°C, and the reaction was carried out at 800 rpm for 6 h, the temperature was raised to 180°C, esterification was carried out at 0.09 MPa for 3 h, and itaconic acid-based unsaturated polyester was prepared; triethylamine, bis(3-mercaptopropionic acid) ethylene glycol and acetone were mixed in a mass ratio of 0.22:22:20, uniformly dispersed, 0.6 times the molar mass of bis(3-mercaptopropionic acid) ethylene glycol of isocyanate was added, the reaction was carried out at room temperature and 800 rpm for 12 h, vacuum distillation was carried out and precipitated with ethyl ether, suction filtration was carried out, washed with ethyl ether 3 times, and vacuum dried at 25°C, to prepare mercaptoisocyanate; under a nitrogen atmosphere, itaconic acid-based unsaturated polyester and acetone were mixed in a mass ratio of 1:2, stirred uniformly, 0.001 times the mass of itaconic acid-based unsaturated polyester of polymerization inhibitor hydroquinone was added, 0.2 times the mass of itaconic acid-based unsaturated polyester of acrolein was added at a rate of 1 ml / min, 0.002 times the mass of itaconic acid-based unsaturated polyester of catalyst triethylamine was added, the temperature was raised to 80°C, the reaction was carried out for 6 h, vacuum distillation was carried out, precipitated with ethyl ether, mercaptoisocyanate, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and tetrahydrofuran were added, the mass ratio of itaconic acid-based unsaturated polyester, mercaptoisocyanate, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and tetrahydrofuran was 40:12:0.12:0.12, irradiated with a 365 nm UV lamp at 10 mW / cm² for 30 min, dialyzed with a molecular weight cutoff of 1000 Da, and finally freeze-dried at -40°C to prepare epoxy itaconic acid-based unsaturated polyester;

[0035] S2. Polyethylene glycol, benzyl triethyl ammonium chloride and 10% sodium hydroxide solution by mass fraction were mixed in a mass ratio of 100:0.05:8, heated to 45°C, stirred uniformly, and then 0.2 times the mass of polyethylene glycol of epichlorohydrin was added at a rate of 1 ml / min, reacted for 3h, and then distilled under reduced pressure, and the pH was adjusted to 6.8 with hydrochloric acid, filtered, and then added with acetone, 3-mercaptopropionic acid and catalyst triethylamine, the mass ratio of polyethylene glycol, acetone, 3-mercaptopropionic acid and catalyst triethylamine being 100:20:12:0.2, stirred at 200 rpm at room temperature for 18h, terminated with ice water, extracted with diethyl ether, distilled under reduced pressure, to obtain modified polyethylene glycol; polyamide, modified polyethylene glycol, epoxy itaconic acid-based unsaturated polyester and compatible agent maleic anhydride grafted polyethylene were mixed in a mass ratio of 70:18:9:2 and placed in a twin-screw extruder, melt extruded and granulated, the temperature of the feeding section was 240°C, the temperature of the melting section was 250°C, the temperature of the mixing section was 260°C, the temperature of the die head was 255°C, the screw rotation speed was 120 rpm, the residence time was 3 min, and then melt spinning was carried out in a melt spinning machine after water cooling and granulation, the spinning temperature was 265°C, to obtain modified polyamide fibers, which were woven into clothing fabric;

[0036] S3. In a nitrogen atmosphere, o-allyl phenol and dimethyl formamide were mixed in a mass ratio of 1:5, heated to 60°C, and then 0.018 times the mass of o-allyl phenol of catalyst potassium hydroxide and 0.012 times the mass of o-allyl phenol of catalyst tetrabutyl ammonium bromide were added, stirred uniformly, and then 0.71 times the mass of o-allyl phenol of 1,3-bis(chloromethyl)tetramethyldisiloxane was added at a rate of 1 ml / min, heated to 80°C, refluxed for 8h, cooled to room temperature, the pH was adjusted to 6.8 with hydrochloric acid, filtered and distilled under reduced pressure, extracted with diethyl ether, dried with anhydrous sodium sulfate, and rotary evaporated, to obtain allyl siloxane; allyl siloxane, formic acid, toluene and concentrated sulfuric acid were mixed in a mass ratio of 40:100:10:1, stirred uniformly, and then 0.1 times the mass of allyl siloxane of 30% hydrogen peroxide solution by mass fraction was added at a rate of 1 ml / min, heated to 60°C, reacted for 6h, quenched with ice water, washed with saturated sodium bicarbonate solution for 3 times, dried with anhydrous sodium sulfate, and distilled under reduced pressure, to obtain epoxy allyl siloxane;

[0037] S4. Under nitrogen atmosphere, mix malonic acid, methyl allyl alcohol polyoxyethylene ether and acetone in a mass ratio of 3:7:10, heat to 60℃, stir until uniform, then add 0.01 times the mass of catalyst p-toluenesulfonic acid, keep the temperature and stir at 200 rpm for 4h, adjust the pH to 6 with 10% sodium hydroxide solution, distill under reduced pressure, then wash with ether 3 times, to obtain carboxyl polyoxyethylene ether; under nitrogen atmosphere, mix carboxyl polyoxyethylene ether and acetone in a mass ratio of 1:4, heat to 60℃, stir until dissolved, then add 0.02 times the mass of catalyst triethylamine, stir until uniform, then add 1.1 times the mass of carboxyl polyoxyethylene ether, heat to 80℃, react for 6h, adjust the pH to 6.8 with hydrochloric acid, to obtain the finishing agent;

[0038] S5. Dip the garment fabric in the finishing agent, with a bath ratio of 1:10, heat to 80℃, dip for 30-50min, spin dry, then dry at 110℃, to obtain the antibacterial functional garment fabric.

[0039] Example 2

[0040] The preparation method of the antibacterial functional garment fabric in this example is as follows:

[0041] S1. Under a nitrogen atmosphere, 1,4-butanedioic acid, itaconic acid and 1,4-butanediol were mixed in a molar ratio of 3:7:10.5, stirred uniformly, 0.02 times the mass of itaconic acid of catalyst tetrabutyl titanate and 0.025 times the mass of itaconic acid of polymerization inhibitor hydroquinone were added, the temperature was raised to 171℃, and the reaction was carried out at 1000 rpm for 7h, the temperature was raised to 181℃, esterification was carried out at 0.094 MPa for 3.5h, to obtain itaconic acid-based unsaturated polyester; triethylamine, bis(3-mercaptopropionic acid) ethylene glycol and acetone were mixed in a mass ratio of 0.27:27:30, uniformly dispersed, 0.7 times the molar mass of bis(3-mercaptopropionic acid) ethylene glycol of isocyanate was added, the reaction was carried out at room temperature and 1000 rpm for 13h, distilled under reduced pressure and precipitated with ethyl ether, filtered, washed with ethyl ether 4 times, and dried at 30℃ under vacuum, to obtain mercaptoisocyanate; under a nitrogen atmosphere, itaconic acid-based unsaturated polyester and acetone were mixed in a mass ratio of 1:2.5, stirred uniformly, 0.002 times the mass of itaconic acid-based unsaturated polyester of polymerization inhibitor hydroquinone was added, 0.25 times the mass of itaconic acid-based unsaturated polyester of acrolein was added at a rate of 2ml / min, 0.003 times the mass of itaconic acid-based unsaturated polyester of catalyst triethylamine was added, the temperature was raised to 85℃, the reaction was carried out for 7h, distilled under reduced pressure, precipitated with ethyl ether, and then mercaptoisocyanate, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and tetrahydrofuran were added, the mass ratio of itaconic acid-based unsaturated polyester, mercaptoisocyanate, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and tetrahydrofuran was 40:13.5:0.12:0.12, irradiated with a 365nm UV lamp at 10mW / cm² for 40min, dialyzed with a molecular weight cutoff of 1000Da, and finally freeze-dried at -50℃, to obtain epoxy itaconic acid-based unsaturated polyester;

[0042] S2. Polyethylene glycol, benzyltriethylammonium chloride and 20% by mass sodium hydroxide solution were mixed in a mass ratio of 100:0.23:9, and heated to 50°C. After stirring uniformly, 0.21 times the mass of polyethylene glycol of epichlorohydrin was added dropwise at a rate of 2 ml / min, and reacted for 3.5 h. After distillation under reduced pressure and adjustment of pH to 7.0 with hydrochloric acid, filtration was performed, and acetone, 3-mercaptopropionic acid and a catalyst triethylamine were added in a mass ratio of 100:25:14:0.3. After stirring at 300 rpm at room temperature for 22 h, the reaction was terminated with ice water, and extracted with diethyl ether. After distillation under reduced pressure, modified polyethylene glycol was prepared. Polyamide, modified polyethylene glycol, epoxy itaconic acid-based unsaturated polyester and a compatible agent maleic anhydride grafted polyethylene were mixed in a mass ratio of 70:18:11:2, and melt extruded and granulated in a twin-screw extruder. The temperature of the feeding section was 241°C, the temperature of the melting section was 251°C, the temperature of the mixing section was 261°C, the temperature of the die head was 256°C, the screw rotation speed was 140 rpm, and the residence time was 4 min. After water cooling and pelletization, melt spinning was performed in a melt spinning machine at a spinning temperature of 266°C, and modified polyamide fibers were prepared. The fibers were woven into a garment fabric.

[0043] S3. In a nitrogen atmosphere, o-allylphenol and dimethylformamide were mixed in a mass ratio of 1:5.5, and heated to 65°C. After stirring uniformly, 0.020 times the mass of o-allylphenol of a catalyst potassium hydroxide and 0.013 times the mass of o-allylphenol of a catalyst tetrabutylammonium bromide were added, and 0.72 times the mass of o-allylphenol of 1,3-bis(chloromethyl)tetramethyldisiloxane was added dropwise at a rate of 2 ml / min. After heating to 81°C, reflux was performed for 12 h, and the reaction was cooled to room temperature. After adjustment of pH to 7.0 with hydrochloric acid, filtration was performed, and distillation under reduced pressure, extraction with diethyl ether, drying with anhydrous sodium sulfate, and rotary evaporation were performed, and allylsiloxane was prepared. Allylsiloxane, formic acid, toluene and concentrated sulfuric acid were mixed in a mass ratio of 50:100:10:1.5, and stirred uniformly. After dropwise addition of 0.2 times the mass of allylsiloxane of a 30% by mass hydrogen peroxide solution at a rate of 2 ml / min, heating was performed to 62°C, and the reaction was performed for 6.5 h. After quenching with ice water, washing was performed 4 times with saturated sodium bicarbonate solution, drying was performed with anhydrous sodium sulfate, and distillation under reduced pressure was performed, and epoxy allylsiloxane was prepared.

[0044] S4. Under nitrogen atmosphere, mix malonic acid, methyl alkenyl alcohol polyoxyethylene ether and acetone in a mass ratio of 3:7.5:10, heat to 70℃, stir until uniform, then add 0.015 times the mass of catalyst p-toluenesulfonic acid, keep the temperature and stir at 240 rpm for 5h, adjust the pH to 6.5 with 10% sodium hydroxide solution, distill under reduced pressure, then wash with ether 4 times, to obtain carboxyl polyoxyethylene ether; under nitrogen atmosphere, mix carboxyl polyoxyethylene ether and acetone in a mass ratio of 1:5, heat to 65℃, stir until dissolved, then add 0.025 times the mass of catalyst triethylamine, stir until uniform, then add 1.15 times the mass of carboxyl polyoxyethylene ether of epoxy alkenyl siloxane, heat to 85℃, react for 7h, adjust the pH to 7.0 with hydrochloric acid, to obtain the finishing agent;

[0045] S5. Dip the garment fabric in the finishing agent, with a bath ratio of 1:11, heat to 85℃, dip for 40min, spin dry, then dry at 120℃, to obtain the antibacterial functional garment fabric.

[0046] Example 3

[0047] The preparation method of the antibacterial functional garment fabric in this example is:

[0048] S1. Under a nitrogen atmosphere, 1,4-butanedioic acid, itaconic acid and 1,4-butanediol were mixed in a molar ratio of 3:7:11, stirred uniformly, 0.03 times the mass of itaconic acid of catalyst tetrabutyl titanate and 0.03 times the mass of itaconic acid of polymerization inhibitor hydroquinone were added, the temperature was raised to 172°C, and the reaction was carried out at 1200 rpm for 8 h, the temperature was raised to 182°C, esterification was carried out at 0.095 MPa for 4 h, and an itaconic acid-based unsaturated polyester was prepared; triethylamine, bis(3-mercaptopropionic acid) ethylene glycol and acetone were mixed in a mass ratio of 0.32:32:40, uniformly dispersed, 0.8 times the molar mass of bis(3-mercaptopropionic acid) ethylene glycol of isocyanate was added, the reaction was carried out at room temperature and 1200 rpm for 15 h, vacuum distillation was carried out and precipitated with ethyl ether, suction filtration was carried out, washed with ethyl ether 5 times, and vacuum dried at 35°C, and a mercaptoisocyanate was prepared; under a nitrogen atmosphere, the itaconic acid-based unsaturated polyester and acetone were mixed in a mass ratio of 1:3, the temperature was raised to 70°C, and after stirring uniformly, 0.003 times the mass of itaconic acid-based unsaturated polyester of polymerization inhibitor hydroquinone was added, 0.3 times the mass of itaconic acid-based unsaturated polyester of acrolein was added at a rate of 3 ml / min, 0.004 times the mass of itaconic acid-based unsaturated polyester of catalyst triethylamine was added, the temperature was raised to 90°C, the reaction was carried out for 8 h, vacuum distillation was carried out, precipitated with ethyl ether, and the mercaptoisocyanate, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and tetrahydrofuran were added, the mass ratio of itaconic acid-based unsaturated polyester, mercaptoisocyanate, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and tetrahydrofuran was 40:13:0.12:0.12, irradiated with a 365 nm UV lamp at 10 mW / cm² for 50 min, dialyzed with a molecular weight cutoff of 1000 Da, and finally freeze-dried at -60°C, and an epoxy itaconic acid-based unsaturated polyester was prepared;

[0049] S2. Polyethylene glycol, benzyl triethyl ammonium chloride and 30% sodium hydroxide solution by mass fraction were mixed in a mass ratio of 100:0.5:10, heated to 55°C, and stirred uniformly. Then, 0.22 times the mass of polyethylene glycol of epichlorohydrin was added dropwise at a rate of 3 ml / min, reacted for 4 h, and then distilled under reduced pressure. The pH was adjusted to 7.2 with hydrochloric acid, filtered, and then 3-mercaptopropionic acid, acetone and a catalyst triethylamine were added in a mass ratio of 100:30:15:0.4. The mixture was stirred at 400 rpm at room temperature for 24 h, the reaction was terminated with ice water, extracted with diethyl ether, and distilled under reduced pressure to obtain modified polyethylene glycol. Polyamide, modified polyethylene glycol, epoxy itaconic acid-based unsaturated polyester and compatible agent maleic anhydride grafted polyethylene were mixed in a mass ratio of 70:18:13:2 and placed in a twin-screw extruder for melt extrusion and granulation. The temperature of the feeding section was 242°C, the temperature of the melting section was 252°C, the temperature of the mixing section was 262°C, the temperature of the die head was 257°C, the screw rotation speed was 150 rpm, the residence time was 5 min, and then the product was placed in a melt spinning machine for melt spinning after water cooling and granulation. The spinning temperature was 268°C, and a modified polyamide fiber was obtained. The fiber was woven into a garment fabric.

[0050] S3. In a nitrogen atmosphere, o-allyl phenol and dimethyl formamide were mixed in a mass ratio of 1:6, heated to 70°C, and then 0.022 times the mass of o-allyl phenol of a catalyst potassium hydroxide and 0.014 times the mass of o-allyl phenol of a catalyst tetrabutylammonium bromide were added. The mixture was stirred uniformly, and then 0.73 times the mass of o-allyl phenol of 1,3-bis(chloromethyl)tetramethyldisiloxane was added dropwise at a rate of 3 ml / min. The temperature was increased to 82°C, and the mixture was refluxed for 16 h. The mixture was cooled to room temperature, the pH was adjusted to 7.2 with hydrochloric acid, filtered, distilled under reduced pressure, extracted with diethyl ether, dried with anhydrous sodium sulfate, and rotary evaporated to obtain allyl siloxane. Allyl siloxane, formic acid, toluene and concentrated sulfuric acid were mixed in a mass ratio of 60:100:10:2, stirred uniformly, and then 0.3 times the mass of allyl siloxane of a 30% hydrogen peroxide solution was added dropwise at a rate of 3 ml / min. The temperature was increased to 63°C, and the mixture was reacted for 7 h. The reaction was quenched with ice water, washed with saturated sodium bicarbonate solution 5 times, dried with anhydrous sodium sulfate, and distilled under reduced pressure to obtain epoxy allyl siloxane.

[0051] S4. Under nitrogen atmosphere, mix malonic acid, methyl allyl alcohol polyoxyethylene ether and acetone in a mass ratio of 3:8:10, heat to 80℃, stir until uniform, then add 0.02 times the mass of catalyst p-toluenesulfonic acid, keep the temperature and stir at 300 rpm for 6 h, adjust the pH to 7 with 10% sodium hydroxide solution, distill under reduced pressure, then wash with diethyl ether 5 times, to obtain carboxyl polyoxyethylene ether; under nitrogen atmosphere, mix the carboxyl polyoxyethylene ether and acetone in a mass ratio of 1:6, heat to 70℃, stir until dissolved, then add 0.03 times the mass of catalyst triethylamine, stir until uniform, then add 1.2 times the mass of carboxyl polyoxyethylene ether of epoxy allyl siloxane, heat to 90℃, react for 8 h, adjust the pH to 7.2 with hydrochloric acid, to obtain the finishing agent;

[0052] S5. Dip the garment fabric in the finishing agent, with a bath ratio of 1:12, heat to 90℃, dip for 50 min, spin dry, then dry at 130℃, to obtain the antibacterial functional garment fabric.

[0053] Comparative Example 1

[0054] The preparation method of Comparative Example 1 is the same as that of Example 2. The difference between the antibacterial functional garment fabric of Comparative Example 1 and that of Example 2 is that the modified polyamide is only polyamide, and the modified polyethylene glycol is melted to obtain.

[0055] Comparative Example 2

[0056] The preparation method of Comparative Example 2 is the same as that of Example 2. The difference between the antibacterial functional garment fabric of Comparative Example 2 and that of Example 2 is that the modified polyamide is only polyamide and epoxy itaconic acid-based unsaturated polyester, which are melted to obtain.

[0057] Comparative Example 3

[0058] The preparation method of Comparative Example 3 is the same as that of Example 2. The difference between the antibacterial functional garment fabric of Comparative Example 3 and that of Example 2 is that the fiber fabric is only polyamide fiber textile.

[0059] Comparative Example 4

[0060] The preparation method of Comparative Example 4 is the same as that of Example 2. The difference between the antibacterial functional garment fabric of Comparative Example 4 and that of Example 2 is that the finishing agent is only epoxy allyl siloxane.

[0061] Comparative Example 5

[0062] The preparation method of Comparative Example 5 is the same as that of Example 2. The difference between the antibacterial functional garment fabric of Comparative Example 5 and that of Example 2 is that the antibacterial functional garment fabric is only a fiber fabric made of modified polyamide fiber textile;

[0063] Effect Example

[0064] The following Table 1 shows the performance analysis results of the antibacterial functional clothing fabric prepared by using the examples 1 to 3 and the comparative examples 1 to 5 of the present application.

[0065] Table 1

[0066]

[0067] It can be obviously found from the comparison of the experimental data of the examples and the comparative examples in Table 1 that the antibacterial functional clothing fabric prepared by using examples 1, 2 and 3 has excellent mechanical properties, hydrophilicity, antistatic property and wear resistance.

[0068] It can be found from the comparison of the experimental data of example 1, example 2, example 3 and comparative example 1, comparative example 2 and comparative example 3 that the modified polyamide fiber prepared by melt spinning of polyamide, modified polyvinyl alcohol and epoxy itaconic acid-based unsaturated polyester has intermolecular interaction and forms a complex crosslinked structure, which not only improves the mechanical strength of the fiber, but also has antibacterial function. The hydroxyl and mercapto groups on the modified polyamide fiber can also react with the finishing agent, so that the finishing agent is tightly combined with the fiber molecules to enhance the adhesion.

[0069] It can be found from the comparison of the experimental data of example 1, example 2, example 3 and comparative example 4, comparative example 5 that the carboxyl polyoxyethylene ether with carboxyl group is reacted with epoxy allyl siloxane to form a siloxane finishing agent with polyoxyethylene ether, which improves the hydrophilicity and makes the fabric have both hydrophilicity and antistatic property. The fabric after finishing with the finishing agent also forms a dense protective film on the surface, which enhances the wear resistance of the fabric.

[0070] Obviously, the above embodiments are only examples for clearly illustrating the embodiments of the present application, and are not intended to limit the embodiments of the present application. For those skilled in the art, other different forms of changes or variations can be made on the basis of the above description. Here, it is not necessary and impossible to exhaust all the embodiments. The obvious changes or variations extended from the spirit of the present application are still within the protection scope of the present application.

Claims

1. An antibacterial functional clothing fabric, characterized by, The fiber fabric is prepared by impregnating the fiber fabric with a finishing agent; the fiber fabric is prepared by spinning modified polyamide fibers; the finishing agent is prepared by reacting epoxy allyl siloxane with carboxyl polyoxyethylene ether; the preparation method of the modified polyamide fibers is as follows: polyamide, modified polyethylene glycol, epoxy itaconic acid-based unsaturated polyester and compatible agent maleic anhydride graft polyethylene are mixed according to a mass ratio of 70:18:9-13:2 and placed in a double-screw extruder, melt extrusion granulation, the temperature of the feeding section is 240-242 DEG C, the temperature of the melting section is 250-252 DEG C, the temperature of the mixing section is 260-262 DEG C, the temperature of the head is 255-257 DEG C, the screw rotation speed is 120-150 rpm, the residence time is 3-5 min, after water cooling and granulation, the modified polyamide fibers are prepared by melt spinning in a melt spinning machine, the spinning temperature is 265-268 DEG C; the preparation method of the epoxy allyl siloxane is as follows: allyl siloxane, formic acid, toluene and concentrated sulfuric acid are mixed according to a mass ratio of 40-60:100:10:1-2, after stirring uniformly, 0.1-0.3 times of the mass fraction of 30% hydrogen peroxide solution of the mass of allyl siloxane is added at a rate of 1-3 ml / min, the temperature is raised to 60-63 DEG C, the reaction is carried out for 6-7 h, the reaction is quenched with ice water, washed with saturated sodium bicarbonate solution for 3-5 times, dried with anhydrous sodium sulfate, and distilled under reduced pressure to prepare epoxy allyl siloxane; the preparation method of the carboxyl polyoxyethylene ether is as follows: under a nitrogen atmosphere, tricarballylic acid, methyl allyl alcohol polyoxyethylene ether and acetone are mixed according to a mass ratio of 3:7-8:10, the temperature is raised to 60-80 DEG C, after stirring uniformly, 0.01-0.02 times of the catalyst p-toluenesulfonic acid of the mass of tricarballylic acid is added, the reaction is carried out at 200-300 rpm for 4-6 h, the pH is adjusted to 6-7 with 10% sodium hydroxide solution, distilled under reduced pressure, washed with diethyl ether for 3-5 times to prepare carboxyl polyoxyethylene ether.

2. The antibacterial functional clothing fabric according to claim 1, characterized in that, The epoxy itaconic acid-based unsaturated polyester is prepared by reacting itaconic acid-based unsaturated polyester with propylene aldehyde, and then reacting with mercapto isocyanate; the mercapto isocyanate is prepared by reacting bis(3-mercaptopropionic acid) ethylene with isocyanate.

3. The method of claim 1, wherein the fabric is prepared by the steps of: (a) preparing a solution of the antimicrobial agent; (b) applying the solution to the fabric; (c) drying the fabric; and (d) washing the fabric. The method comprises the following specific steps: S1. Under the atmosphere of nitrogen, the itaconic acid-based unsaturated polyester is mixed with acetone at a mass ratio of 1:2-3, and heated to 60-70℃. After stirring uniformly, 0.001-0.003 times the mass of the itaconic acid-based unsaturated polyester of the polymerization inhibitor hydroquinone is added, and 0.2-0.3 times the mass of the itaconic acid-based unsaturated polyester of acrolein, 0.002-0.004 times the mass of the itaconic acid-based unsaturated polyester of the catalyst triethylamine are added dropwise at a rate of 1-3 ml / min. The temperature is raised to 80-90℃, and the reaction is carried out for 6-8 h. After distillation under reduced pressure, precipitation with diethyl ether is performed, and then mercaptoisocyanate, a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and tetrahydrofuran are added. The mass ratio of the itaconic acid-based unsaturated polyester, mercaptoisocyanate, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and tetrahydrofuran is 40:12-13:0.12:0.

12. Irradiation is performed with a 365 nm UV lamp at 10 mW / cm² for 30-50 min. After dialysis with a molecular weight cutoff of 1000 Da, freeze-drying is finally carried out at -40--60℃ to obtain an epoxy itaconic acid-based unsaturated polyester; S2. The polyamide, modified polyethylene glycol, epoxy itaconic acid-based unsaturated polyester and compatible agent maleic anhydride grafted polyethylene are mixed at a mass ratio of 70:18:9-13:2 and placed in a twin-screw extruder for melt extrusion and granulation. The temperature of the feeding section is 240-242℃, the temperature of the melting section is 250-252℃, the temperature of the mixing section is 260-262℃, the temperature of the die head is 255-257℃, the screw rotation speed is 120-150 rpm, the residence time is 3-5 min, and the granules are then placed in a melt spinning machine for melt spinning after water cooling and cutting. The spinning temperature is 265-268℃, and a modified polyamide fiber is obtained. The fiber is woven into a garment fabric; S3. Allyl siloxane, formic acid, toluene and concentrated sulfuric acid are mixed at a mass ratio of 40-60:100:10:1-2, and stirred uniformly. Then, 0.1-0.3 times the mass of the allyl siloxane of a 30% hydrogen peroxide solution is added dropwise at a rate of 1-3 ml / min, and the temperature is raised to 60-63℃. The reaction is carried out for 6-7 h, and then quenched with ice water. The solution is washed with saturated sodium bicarbonate solution for 3-5 times, dried with anhydrous sodium sulfate, and distilled under reduced pressure to obtain epoxy allyl siloxane; S4. Under the atmosphere of nitrogen, the carboxyl polyoxyethylene ether is mixed with acetone at a mass ratio of 1:4-6, and heated to 60-70℃. After stirring and dissolving, 0.02-0.03 times the mass of the carboxyl polyoxyethylene ether of the catalyst triethylamine is added, and stirred uniformly. Then, 1.1-1.2 times the mass of the carboxyl polyoxyethylene ether of the epoxy allyl siloxane is added, and the temperature is raised to 80-90℃. The reaction is carried out for 6-8 h, and then the pH is adjusted to 6.8-7.2 with hydrochloric acid to obtain a finishing agent; S5. The garment fabric is immersed in the finishing agent at a bath ratio of 1:10-12, and heated to 80-90℃. The immersion treatment is carried out for 30-50 min, and then the fabric is spun dry. Finally, the fabric is dried at 110-130℃ to obtain an antibacterial functional garment fabric.

4. The method of claim 3, wherein the fabric is prepared by the steps of: (a) preparing a solution of the antimicrobial agent; (b) applying the solution to the fabric; (c) drying the fabric; and (d) washing the fabric. In step S1, the preparation method of the itaconic acid-based unsaturated polyester is as follows: 1,4-butanedioic acid, itaconic acid and 1,4-butanediol are mixed in a molar ratio of 3:7:10-11 under a nitrogen atmosphere, stirred uniformly, 0.01-0.03 times the mass of the itaconic acid of a catalyst tetrabutyl titanate and 0.02-0.03 times the mass of the itaconic acid of a polymerization inhibitor hydroquinone are added, the temperature is raised to 170-172℃, and the reaction is stirred at 800-1200 rpm for 6-8 h, the temperature is raised to 180-182℃, esterification is carried out at 0.09-0.095 MPa, and the reaction is carried out for 3-4 h to obtain the itaconic acid-based unsaturated polyester.

5. The method of claim 3, wherein the fabric is prepared by the steps of: (a) preparing a solution of the antimicrobial agent; (b) applying the solution to the fabric; (c) drying the fabric; and (d) washing the fabric. In step S1, the preparation method of the mercaptoisocyanate is as follows: triethylamine, bis(3-mercaptopropionic acid) ethylene glycol and acetone are mixed in a mass ratio of 0.22-0.32:22-32:20-40, uniformly dispersed, 0.6-0.8 times the molar mass of bis(3-mercaptopropionic acid) ethylene glycol of isophorone diisocyanate is added, the reaction is stirred at room temperature and 800-1200 rpm for 12-15 h, distilled under reduced pressure and precipitated with ethyl acetate, filtered, washed with ethyl acetate for 3-5 times, dried at 25-35℃ under vacuum, and the mercaptoisocyanate is obtained.

6. The method of claim 3, wherein the fabric is prepared by the steps of: (a) preparing a solution of the antimicrobial agent; (b) applying the solution to the fabric; (c) drying the fabric; and (d) washing the fabric. In step S2, the preparation method of the modified polyethylene glycol is as follows: polyethylene glycol, benzyltriethylammonium chloride and a sodium hydroxide solution with a mass fraction of 10-30% are mixed in a mass ratio of 100:0.05-0.5:8-10, the temperature is raised to 45-55℃, and after being stirred uniformly, 0.2-0.22 times the mass of the polyethylene glycol of epichlorohydrin is added at a rate of 1-3 ml / min, the reaction is carried out for 3-4 h, distilled under reduced pressure, the pH is adjusted to 6.8-7.2 with hydrochloric acid, filtered, acetone, 3-mercaptopropionic acid and a catalyst triethylamine are added, the mass ratio of the polyethylene glycol, acetone, 3-mercaptopropionic acid and the catalyst triethylamine is 100:20-30:12-15:0.2-0.4, the reaction is stirred at room temperature and 200-400 rpm for 18-24 h, the reaction is terminated with ice water, extracted with ethyl acetate, and the modified polyethylene glycol is obtained by distillation under reduced pressure.

7. The method of claim 3, wherein the fabric is prepared by the steps of: (a) preparing a solution of the antimicrobial agent; (b) applying the solution to the fabric; (c) drying the fabric; and (d) washing the fabric. In step S3, the preparation method of the allyl siloxane is as follows: o-allyl phenol and dimethylformamide are mixed in a mass ratio of 1:5-6 under a nitrogen atmosphere, the temperature is raised to 60-70℃, 0.018-0.022 times the mass of the o-allyl phenol of a catalyst potassium hydroxide and 0.012-0.014 times the mass of the o-allyl phenol of a catalyst tetrabutylammonium bromide are added, stirred uniformly, 0.71-0.73 times the mass of the o-allyl phenol of 1,3-bis(chloromethyl)tetramethyldisiloxane is added at a rate of 1-3 ml / min, the temperature is raised to 80-82℃, the reaction is carried out under reflux for 8-16 h, the temperature is cooled to room temperature, the pH is adjusted to 6.8-7.2 with hydrochloric acid, filtered and distilled under reduced pressure, extracted with ethyl acetate, dried with anhydrous sodium sulfate, rotary evaporated, and the allyl siloxane is obtained.

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