Ionic liquid impregnated modified antibacterial nylon fiber and preparation method thereof

Abstract

The invention belongs to the technical field of functional modification of fiber materials, and discloses an ionic liquid impregnated modified antibacterial nylon fiber and a preparation method thereof. The preparation method comprises the following steps: mixing an ionic liquid solubilizer, an ionic liquid and water to obtain an ionic liquid antibacterial impregnation liquid; the nylon fibers are soaked in a surfactant solution for surface treatment; carrying out impregnation treatment on the pretreated nylon fiber by adopting the ionic liquid antibacterial impregnation liquid, and drying the impregnated nylon fiber to obtain the ionic liquid impregnated modified antibacterial nylon fiber. The prepared modified antibacterial nylon fiber has broad-spectrum antibacterial performance and a stable antibacterial effect, and particularly has a remarkable antibacterial effect on escherichia coli, the breaking strength and the elongation at break are remarkably improved, and the application range of the antibacterial nylon fiber is widened. Meanwhile, the preparation process of modification is simple, operation is easy and convenient, and industrial production is easy to achieve.

Description

Technical Field

[0001] The invention relates to the technical field of functional modification of fiber materials, and in particular to an ionic liquid impregnated modified antibacterial nylon fiber and a preparation method thereof. Background Art

[0002] As people's demand for comfort and health continues to increase, the antibacterial and antimicrobial nonwoven fabric market is showing a rapid growth trend, especially in the fields of medical and health care, household goods, and automotive interiors, where the market demand has increased significantly. Since there are no antibacterial and antimicrobial functional groups in nylon fiber (also known as polyamide fiber) molecules, the application scope of nylon fiber is limited to a certain extent.

[0003] At present, antibacterial modification methods of nylon fibers have been reported, but most of them have problems such as unstable antibacterial effect, complex modification process and high cost. Summary of the invention

[0004] The purpose of the present invention is to provide an ionic liquid impregnated modified antibacterial nylon fiber and a preparation method thereof, so as to solve the problems of the existing nylon fiber antibacterial modification method, such as unstable antibacterial effect, complex modification process and high cost.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing an ionic liquid impregnated modified antibacterial nylon fiber, comprising the following steps:

[0007] (1) mixing an ionic liquid solubilizing agent, an ionic liquid and water to obtain an ionic liquid antibacterial impregnation solution;

[0008] (2) immersing the nylon fiber in a surfactant solution for surface treatment to obtain pretreated nylon fiber;

[0009] (3) impregnating the pretreated nylon fiber in step (2) with the ionic liquid antibacterial impregnation solution in step (1), and drying the impregnated nylon fiber to obtain the ionic liquid impregnated modified antibacterial nylon fiber;

[0010] There is no order restriction for step (1) and step (2);

[0011] The cation of the ionic liquid in step (1) includes an imidazolium cation, a quaternary ammonium salt cation, a guanidine cation or a quaternary phosphonium salt cation;

[0012] The anion of the ionic liquid in step (1) comprises chloride ion, bromide ion, iodide ion, hydroxide ion, carbonate ion, bicarbonate ion, fluoroborate ion, hexafluorophosphate ion, bis(fluorosulfonyl)imide ion, bistrifluoromethanesulfonylimide ion, hexafluoroantimonate ion, bistrifluoromethanesulfonyl ion, acetate ion, lysine ion, glutamate ion, glycine ion or alanine ion;

[0013] The imidazolium cation includes a di-substituted imidazolium cation, a ternary substituted imidazolium cation or a quaternary substituted imidazolium cation;

[0014] The dibasic substituted imidazolium cation includes 1,3-dimethylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-allyl-3-methylimidazolium cation, 1-butyl-3-ethylimidazolium cation, 1-benzyl-3-methylimidazolium cation, 1-butyl-3-allylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-hexadecyl-3-methylimidazolium cation, 1-eicosyl-3-methylimidazolium cation, N-methylimidazolium cation, N-butylimidazolium cation, N-dodecylimidazolium cation, 1-aminoethyl-3-methylimidazolium cation, 1-aminopropyl-3-methylimidazolium cation, bisaminoethylimidazolium cation or bisaminopropylimidazolium cation;

[0015] The ternary substituted imidazolium cation includes 1,2,3-trimethylimidazolium cation, 1,3,4-trimethylimidazolium cation, 1,3-dibutyl-2-methylimidazolium cation, 1-butyl-3,4-dimethylimidazolium cation, 1-dodecyl-3,4-dimethylimidazolium cation, 1-dodecyl-2,3-dimethylimidazolium cation, 1-butyl-3,4-dimethylimidazolium cation, 1-benzyl-3,4-dimethylimidazolium cation, 1-benzyl-2,3-dimethylimidazolium cation, 1-benzyl-3,4-dodecylimidazolium cation, 1-butyl-3,4-dipropylimidazolium cation, 1-dodecyl-3,4-dibutylimidazolium cation, 1-benzyl-3,4-hexadecylimidazolium cation or 1-benzyl-2,3-dibutylimidazolium cation;

[0016] The quaternary substituted imidazolium cation includes 1,3,4,5-tetramethylimidazolium cation, 1,4,5-trimethyl-3-butylimidazolium cation, 1-methyl-3,4,5-tributylimidazolium cation, 1-methyl-3,4,5-trihexylimidazolium cation or 1-methyl-4,5-dibutyl-3-hexylimidazolium cation;

[0017] The quaternary ammonium salt cations include N,N,N-tri(ethyl)methylammonium cations, N,N,N-tri(n-butyl)methylammonium cations, dodecyldimethylbenzylammonium cations, dodecyltrimethylammonium cations, tetradecyldimethylbenzylammonium cations, cyanoquaternary ammonium salt cations, di-C8 alkylquaternary ammonium cations, polynitrogen heterocyclic quaternary ammonium cations or monoaminated quaternary ammonium cations;

[0018] The guanidine cations include long-chain alkylguanidine cations or biguanidine cations;

[0019] The long-chain alkylguanidine cation includes a dodecylguanidine cation, an octaguanidine acetate cation, a biguanide cation or a polyhexamethyleneguanidine cation;

[0020] The biguanide cation includes a polyhexamethylene biguanide cation or a polyaminopropyl biguanide cation;

[0021] The quaternary phosphonium salt cations include triethyl (methyl) phosphonium cation, tri-n-butyl (methyl) phosphonium cation, tripropyl (methyl) phosphonium cation, tri-n-hexyl (methyl) phosphonium cation, tri-n-octyl (methyl) phosphonium cation, tri-n-dodecyl (methyl) phosphonium cation, dihexyl (ethyl) (methyl) phosphonium cation, di-n-butyl (ethyl) (methyl) phosphonium cation, tri-dodecyl (methyl) phosphonium cation, di-hexadecyl di-ethyl phosphonium cation, tetra-n-butyl phosphonium cation, tetra-n-hexyl phosphonium cation, tetra-hexadecyl phosphonium cation, tetra-dodecyl phosphonium cation, tri-dodecyl (ethyl) phosphonium cation or tri-dodecyl (n-butyl) phosphonium cation.

[0022] Preferably, in the preparation method, the ionic liquid solubilizer in step (1) includes piperazine or m-phenylenediamine; in the ionic liquid antibacterial impregnation solution in step (1), the mass concentration of the ionic liquid solubilizer is 0.3-1.5%, and the mass concentration of the ionic liquid is 0.5-3%.

[0023] Preferably, in the preparation method, the ionic liquid in step (1) includes 1-ethyl-3-methylimidazolium glycine salt, 1-aminopropyl-3-methylimidazolium glycine salt, 1-aminopropyl-3-methylimidazolium alanine salt, bisaminoethylimidazolium bistrifluoromethanesulfonyl imide salt or bisaminopropylimidazolium bistrifluoromethanesulfonyl imide salt.

[0024] Preferably, in the preparation method, in step (2), the surfactant in the surfactant solution includes sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate or sulfonated polyether, the mass concentration of the surfactant solution is 0.1-0.5%, and the mass-to-volume ratio of the nylon fiber to the surfactant solution is 5-15 mg:1 mL.

[0025] Preferably, in the preparation method, the surface treatment time in step (2) is 5 to 10 minutes.

[0026] Preferably, in the preparation method, the mass-to-volume ratio of the pretreated nylon fiber in step (3) to the ionic liquid antibacterial impregnation solution is 2-10 mg:1 mL.

[0027] Preferably, in the preparation method, the temperature of the immersion treatment in step (3) is room temperature and the time is 5 to 10 minutes.

[0028] Preferably, in the preparation method, in step (3), the drying temperature is 90 to 120° C. and the drying time is 5 to 20 min.

[0029] The invention also provides an ionic liquid impregnated modified antibacterial nylon fiber prepared by the preparation method.

[0030] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) As a green organic antibacterial agent, ionic liquid has good thermal stability and low volatility and will not pollute the environment. The present invention selects ionic liquids such as imidazole salts as antibacterial agents, and adopts an impregnation method to prepare modified nylon fibers. The ionic liquid is carried on the surface of the nylon fibers to make them antibacterial. The cationic groups of the ionic liquid on the surface of the modified antibacterial nylon fibers interact electrostatically with the bacterial cell wall to destroy the cell membrane, causing the internal nutrients of the bacteria to flow out, thereby causing the death of the microorganisms and achieving a significant antibacterial effect. The modified antibacterial nylon fiber prepared by the present invention has a broad-spectrum antibacterial property, can effectively inhibit the growth and reproduction of bacteria, and has a significant antibacterial effect on Escherichia coli; at the same time, by adjusting the type and concentration of the ionic liquid, the antibacterial properties of the nylon fiber can also be precisely controlled. Moreover, although the immersion time of the modified antibacterial nylon fiber is short during preparation, the ionic liquid still adheres to the surface of the nylon fiber after high-temperature treatment and has a stable antibacterial effect. This is because the nylon molecular chain contains polar amide bonds, which have good compatibility with ionic liquids. The cations in the ionic liquid easily combine with the nitrogen atoms on the amide, so that the nylon fiber surface carries the ionic liquid. After high-temperature treatment, it still has an antibacterial effect, which greatly broadens the application market of antibacterial nylon fibers.

[0032] (2) The breaking strength of the modified antibacterial nylon fiber prepared by the present invention is significantly improved. This is because the number of molecular chains that bear the applied tension of the fiber increases, and the addition of ionic liquid increases the number of molecular chains that bear the longitudinal force of the fiber and increases the overall strength of the filament, thereby improving the breaking strength of the fiber. At the same time, the molecular chains are arranged more regularly, the ductility is reduced, and the elongation at break is reduced, further expanding the application range of the antibacterial nylon fiber.

[0033] (3) The ionic liquid used in the present invention has a wide range of sources and relatively low cost, which is conducive to reducing production costs. At the same time, the present invention adopts an impregnation method for modification, and the preparation process of the modification is simple, easy to operate, and easy to realize industrial production. DETAILED DESCRIPTION

[0034] The present invention provides a method for preparing an ionic liquid impregnated modified antibacterial nylon fiber, comprising the following steps:

[0035] (1) mixing an ionic liquid solubilizing agent, an ionic liquid and water to obtain an ionic liquid antibacterial impregnation solution;

[0036] (2) immersing the nylon fiber in a surfactant solution for surface treatment to obtain pretreated nylon fiber;

[0037] (3) impregnating the pretreated nylon fiber in step (2) with the ionic liquid antibacterial impregnation solution in step (1), and drying the impregnated nylon fiber to obtain the ionic liquid impregnated modified antibacterial nylon fiber;

[0038] There is no order restriction for step (1) and step (2);

[0039] The cation of the ionic liquid in step (1) includes an imidazolium cation, a quaternary ammonium salt cation, a guanidine cation or a quaternary phosphonium salt cation;

[0040] The anion of the ionic liquid in step (1) comprises chloride ion, bromide ion, iodide ion, hydroxide ion, carbonate ion, bicarbonate ion, fluoroborate ion, hexafluorophosphate ion, bis(fluorosulfonyl)imide ion, bistrifluoromethanesulfonylimide ion, hexafluoroantimonate ion, bistrifluoromethanesulfonyl ion, acetate ion, lysine ion, glutamate ion, glycine ion or alanine ion;

[0041] The imidazolium cation includes a di-substituted imidazolium cation, a ternary substituted imidazolium cation or a quaternary substituted imidazolium cation;

[0042] The dibasic substituted imidazolium cation includes 1,3-dimethylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-allyl-3-methylimidazolium cation, 1-butyl-3-ethylimidazolium cation, 1-benzyl-3-methylimidazolium cation, 1-butyl-3-allylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-hexadecyl-3-methylimidazolium cation, 1-eicosyl-3-methylimidazolium cation, N-methylimidazolium cation, N-butylimidazolium cation, N-dodecylimidazolium cation, 1-aminoethyl-3-methylimidazolium cation, 1-aminopropyl-3-methylimidazolium cation, bisaminoethylimidazolium cation or bisaminopropylimidazolium cation;

[0043] The ternary substituted imidazolium cation includes 1,2,3-trimethylimidazolium cation, 1,3,4-trimethylimidazolium cation, 1,3-dibutyl-2-methylimidazolium cation, 1-butyl-3,4-dimethylimidazolium cation, 1-dodecyl-3,4-dimethylimidazolium cation, 1-dodecyl-2,3-dimethylimidazolium cation, 1-butyl-3,4-dimethylimidazolium cation, 1-benzyl-3,4-dimethylimidazolium cation, 1-benzyl-2,3-dimethylimidazolium cation, 1-benzyl-3,4-dodecylimidazolium cation, 1-butyl-3,4-dipropylimidazolium cation, 1-dodecyl-3,4-dibutylimidazolium cation, 1-benzyl-3,4-hexadecylimidazolium cation or 1-benzyl-2,3-dibutylimidazolium cation;

[0044] The quaternary substituted imidazolium cation includes 1,3,4,5-tetramethylimidazolium cation, 1,4,5-trimethyl-3-butylimidazolium cation, 1-methyl-3,4,5-tributylimidazolium cation, 1-methyl-3,4,5-trihexylimidazolium cation or 1-methyl-4,5-dibutyl-3-hexylimidazolium cation;

[0045] The quaternary ammonium salt cations include N,N,N-tri(ethyl)methylammonium cations, N,N,N-tri(n-butyl)methylammonium cations, dodecyldimethylbenzylammonium cations, dodecyltrimethylammonium cations, tetradecyldimethylbenzylammonium cations, cyanoquaternary ammonium salt cations, di-C8 alkylquaternary ammonium cations, polynitrogen heterocyclic quaternary ammonium cations or monoaminated quaternary ammonium cations;

[0046] The guanidine cations include long-chain alkylguanidine cations or biguanidine cations;

[0047] The long-chain alkylguanidine cation includes a dodecylguanidine cation, an octaguanidine acetate cation, a biguanide cation or a polyhexamethyleneguanidine cation;

[0048] The biguanide cation includes a polyhexamethylene biguanide cation or a polyaminopropyl biguanide cation;

[0049] The quaternary phosphonium salt cations include triethyl (methyl) phosphonium cation, tri-n-butyl (methyl) phosphonium cation, tripropyl (methyl) phosphonium cation, tri-n-hexyl (methyl) phosphonium cation, tri-n-octyl (methyl) phosphonium cation, tri-n-dodecyl (methyl) phosphonium cation, dihexyl (ethyl) (methyl) phosphonium cation, di-n-butyl (ethyl) (methyl) phosphonium cation, tri-dodecyl (methyl) phosphonium cation, di-hexadecyl di-ethyl phosphonium cation, tetra-n-butyl phosphonium cation, tetra-n-hexyl phosphonium cation, tetra-hexadecyl phosphonium cation, tetra-dodecyl phosphonium cation, tri-dodecyl (ethyl) phosphonium cation or tri-dodecyl (n-butyl) phosphonium cation.

[0050] In the present invention, the ionic liquid solubilizer in step (1) preferably includes piperazine or m-phenylenediamine, and more preferably m-phenylenediamine. The function of the ionic liquid solubilizer is that the cations in the ionic liquid (such as polyamino group ionic liquid) can form a complex with the solubilizer to increase its solubility in water.

[0051] In the present invention, the ionic liquid in step (1) preferably includes 1-ethyl-3-methylimidazolium glycine, 1-aminopropyl-3-methylimidazolium glycine, 1-aminopropyl-3-methylimidazolium alanine, bis-aminoethyl imidazolium bis-trifluoromethanesulfonyl imide or bis-aminopropyl imidazolium bis-trifluoromethanesulfonyl imide, and further preferably includes 1-aminopropyl-3-methylimidazolium glycine, 1-aminopropyl-3-methylimidazolium alanine or bis-aminopropyl imidazolium bis-trifluoromethanesulfonyl imide, and more preferably 1-aminopropyl-3-methylimidazolium alanine.

[0052] In the present invention, the mixing temperature in step (1) is preferably 20-40°C, more preferably 25-30°C, and more preferably 25°C.

[0053] In the present invention, in the ionic liquid antibacterial impregnation solution of step (1), the mass concentration of the ionic liquid solubilizing agent is preferably 0.3-1.5%, more preferably 0.6-1.2%, and even more preferably 1%.

[0054] In the present invention, in the ionic liquid antibacterial impregnation solution of step (1), the mass concentration of the ionic liquid is preferably 0.5-3%, more preferably 1-2%, and more preferably 1%.

[0055] In the present invention, the surfactant in the surfactant solution of step (2) preferably includes sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate or sulfonated polyether, and further preferably includes sodium dodecyl sulfonate or sodium dodecylbenzene sulfonate, and further preferably sodium dodecyl sulfonate. The function of the surfactant is to remove dirt from the fiber surface. Taking sodium dodecyl sulfonate as an example, it is an anionic surfactant, the hydrophobic end of the molecule is a straight-chain alkyl containing 12 carbon atoms, which has a strong lipophilicity, and the hydrophilic end is a sulfonate ion, which has good water solubility. After ionization in water, the sulfonate ion carries a negative charge, which makes it have the effects of penetration, wetting, emulsification and decontamination.

[0056] In the present invention, the mass concentration of the surfactant solution in step (2) is preferably 0.1 to 0.5%, more preferably 0.15 to 0.3%, and even more preferably 0.2%.

[0057] In the present invention, the mass-to-volume ratio of the nylon fiber to the surfactant solution in step (2) is preferably 5-15 mg:1 mL, more preferably 6-10 mg:1 mL, and even more preferably 7-8 mg:1 mL.

[0058] In the present invention, the surface treatment time in step (2) is preferably 5 to 10 minutes, more preferably 5 to 8 minutes, and more preferably 5 minutes.

[0059] In the present invention, after the surface treatment in step (2), the process preferably further comprises: washing the surface treated nylon fiber with ethanol and water in sequence, and then drying by ventilation.

[0060] In the present invention, the washing time with ethanol is preferably 5 to 10 min, more preferably 8 to 10 min, and even more preferably 10 min.

[0061] In the present invention, the number of times of washing with water is preferably 2 to 3 times, more preferably 3 times; the time is preferably 5 to 20 minutes, more preferably 5 to 10 minutes, and more preferably 10 minutes.

[0062] In the present invention, the ventilation drying time is preferably 6 to 36 hours, more preferably 12 to 24 hours, and more preferably 24 hours.

[0063] In the present invention, the mass-to-volume ratio of the pretreated nylon fiber in step (3) to the ionic liquid antibacterial impregnation solution is preferably 2-10 mg:1 mL, more preferably 4-8 mg:1 mL, and more preferably 5 mg:1 mL.

[0064] In the present invention, the temperature of the immersion treatment in step (3) is preferably room temperature; the time is preferably 5 to 10 minutes, more preferably 8 to 10 minutes, and more preferably 10 minutes.

[0065] In the present invention, the drying temperature in step (3) is preferably 90-120°C, more preferably 100-110°C, and more preferably 100°C; the drying time is preferably 5-20 min, more preferably 8-15 min, and more preferably 10 min.

[0066] In the present invention, after the drying in step (3), the step preferably further comprises: soaking in water and then drying by ventilation.

[0067] In the present invention, the soaking time in water is preferably 1 to 3 days, more preferably 1 to 2 days, and more preferably 1 day.

[0068] In the present invention, the ventilation drying time is preferably 12 to 26 hours, more preferably 12 to 24 hours, and more preferably 24 hours.

[0069] The invention also provides an ionic liquid impregnated modified antibacterial nylon fiber prepared by the preparation method.

[0070] In the present invention, the amount of ionic liquid added needs to be strictly controlled. Too much or too little addition will affect the antibacterial properties of nylon fiber. Too much addition will cause the fiber to become hard, affecting its softness and comfort; too little addition will fail to achieve the expected antibacterial effect.

[0071] In the present invention, the combination mode of ionic liquid and nylon fiber is also an important factor affecting the antibacterial performance. Since the nylon molecular chain contains polar amide bonds, it has good compatibility with ionic liquids, and the cations in the ionic liquids are easily combined with the nitrogen atoms on the amides, so that the nylon fiber surface carries the ionic liquid. If the combination mode is unreasonable, the ionic liquid will easily fall off, thereby reducing the antibacterial effect.

[0072] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0073] Example 1

[0074] This embodiment provides a method for preparing an ionic liquid-impregnated modified antibacterial nylon fiber, comprising the following steps:

[0075] (1) dissolving m-phenylenediamine and 1-aminopropyl-3-methylimidazolium alanine salt (manufacturer: Xi'an Qiyue Biotechnology Co., Ltd.) in water, stirring evenly at 25° C., to obtain an ionic liquid antibacterial impregnation solution, wherein the concentration of m-phenylenediamine is 1 wt % and the concentration of the ionic liquid is 0.5 wt %;

[0076] (2) Weighing 5 g of nylon fiber, immersing it in a pre-prepared 648 mL, 0.2 wt % sodium dodecyl sulfate aqueous solution, ultrasonically cleaning it for 5 min, then ultrasonically cleaning it with ethanol for 10 min, and finally stirring and cleaning it with deionized water for 3 times, cleaning it for 10 min, and standing it in a fume hood for 24 h to dry, thereby obtaining pretreated nylon fiber;

[0077] (3) 5 g of pretreated nylon fiber was immersed in 1000 mL of ionic liquid antibacterial impregnation solution for 10 min at room temperature, and then vacuum dried in an oven at 100 °C for 10 min; then immersed in deionized water for 1 day, and allowed to stand in a fume hood for 24 h to obtain ionic liquid impregnated modified antibacterial nylon fiber.

[0078] Example 2

[0079] This embodiment provides a method for preparing an ionic liquid-impregnated modified antibacterial nylon fiber, comprising the following steps:

[0080] (1) dissolving m-phenylenediamine and 1-aminopropyl-3-methylimidazolium alanine salt (manufacturer: Xi'an Qiyue Biotechnology Co., Ltd.) in water, and stirring evenly at 25° C. to obtain an ionic liquid antibacterial impregnation solution, wherein the concentration of m-phenylenediamine is 1 wt % and the concentration of the ionic liquid is 1 wt %;

[0081] (2) Weighing 5 g of nylon fiber, immersing it in a pre-prepared 648 mL, 0.2 wt % sodium dodecyl sulfate aqueous solution, ultrasonically cleaning it for 5 min, then ultrasonically cleaning it with ethanol for 10 min, and finally stirring and cleaning it with deionized water for 3 times, cleaning it for 10 min, and standing it in a fume hood for 24 h to dry, thereby obtaining pretreated nylon fiber;

[0082] (3) 5 g of pretreated nylon fiber was immersed in 1000 mL of ionic liquid antibacterial impregnation solution for 10 min at room temperature, and then vacuum dried in an oven at 100 °C for 10 min; then immersed in deionized water for 1 day, and allowed to stand in a fume hood for 24 h to obtain ionic liquid impregnated modified antibacterial nylon fiber.

[0083] Example 3

[0084] This embodiment provides a method for preparing an ionic liquid-impregnated modified antibacterial nylon fiber, comprising the following steps:

[0085] (1) dissolving m-phenylenediamine and 1-aminopropyl-3-methylimidazolium alanine salt (manufacturer: Xi'an Qiyue Biotechnology Co., Ltd.) in water, and stirring evenly at 25° C. to obtain an ionic liquid antibacterial impregnation solution, wherein the concentration of m-phenylenediamine is 1 wt % and the concentration of the ionic liquid is 1.5 wt %;

[0086] (2) Weighing 5 g of nylon fiber, immersing it in a pre-prepared 648 mL, 0.2 wt % sodium dodecyl sulfate aqueous solution, ultrasonically cleaning it for 5 min, then ultrasonically cleaning it with ethanol for 10 min, and finally stirring and cleaning it with deionized water for 3 times, cleaning it for 10 min, and standing it in a fume hood for 24 h to dry, thereby obtaining pretreated nylon fiber;

[0087] (3) 5 g of pretreated nylon fiber was immersed in 1000 mL of ionic liquid antibacterial impregnation solution for 10 min at room temperature, and then vacuum dried in an oven at 100 °C for 10 min; then immersed in deionized water for 1 day, and allowed to stand in a fume hood for 24 h to obtain ionic liquid impregnated modified antibacterial nylon fiber.

[0088] Example 4

[0089] This embodiment provides a method for preparing an ionic liquid-impregnated modified antibacterial nylon fiber, comprising the following steps:

[0090] (1) dissolving m-phenylenediamine and 1-aminopropyl-3-methylimidazolium alanine salt (manufacturer: Xi'an Qiyue Biotechnology Co., Ltd.) in water, and stirring evenly at 25° C. to obtain an ionic liquid antibacterial impregnation solution, wherein the concentration of m-phenylenediamine is 1 wt % and the concentration of the ionic liquid is 2 wt %;

[0091] (2) Weighing 5 g of nylon fiber, immersing it in a pre-prepared 648 mL, 0.2 wt % sodium dodecyl sulfate aqueous solution, ultrasonically cleaning it for 5 min, then ultrasonically cleaning it with ethanol for 10 min, and finally stirring and cleaning it with deionized water for 3 times, cleaning it for 10 min, and standing it in a fume hood for 24 h to dry, thereby obtaining pretreated nylon fiber;

[0092] (3) 5 g of pretreated nylon fiber was immersed in 1000 mL of ionic liquid antibacterial impregnation solution for 10 min at room temperature, and then vacuum dried in an oven at 100 °C for 10 min; then immersed in deionized water for 1 day, and allowed to stand in a fume hood for 24 h to obtain ionic liquid impregnated modified antibacterial nylon fiber.

[0093] Comparative Example 1

[0094] This comparative example provides a method for preparing a modified nylon fiber, comprising the following steps:

[0095] Weigh 5 g of nylon fiber, immerse it in a pre-prepared 648 mL, 0.2 wt% sodium dodecyl sulfate aqueous solution for ultrasonic cleaning for 5 min, then use ethanol for ultrasonic cleaning for 10 min, and finally stir and clean it with deionized water for 3 times, each cleaning for 10 min, and let it stand in a fume hood for 24 h to dry, to obtain modified nylon fiber.

[0096] Example 5

[0097] This embodiment provides a method for preparing an ionic liquid-impregnated modified antibacterial nylon fiber, comprising the following steps:

[0098] (1) dissolving m-phenylenediamine and 1-ethyl-3-methylimidazolyl glycine salt (prepared in the laboratory, the preparation method refers to the prior art "Study on the Interaction between 1-ethyl-3-methylimidazolyl glycine Ionic Liquid and Water" (Min Zhaojun, Li Zhiyong, Zhao Yuling, et al. Chinese Science, 2022, 52(5):743-751)) in water, stirring evenly at 25°C to obtain an ionic liquid antibacterial impregnation solution, wherein the concentration of m-phenylenediamine is 1wt% and the concentration of the ionic liquid is 1wt%;

[0099] (2) Weighing 5 g of nylon fiber, immersing it in a pre-prepared 648 mL, 0.2 wt % sodium dodecyl sulfate aqueous solution, ultrasonically cleaning it for 5 min, then ultrasonically cleaning it with ethanol for 10 min, and finally stirring and cleaning it with deionized water for 3 times, cleaning it for 10 min, and standing it in a fume hood for 24 h to dry, thereby obtaining pretreated nylon fiber;

[0100] (3) 5 g of pretreated nylon fiber was immersed in 1000 mL of ionic liquid antibacterial impregnation solution for 10 min at room temperature, and then vacuum dried in an oven at 100 °C for 10 min; then immersed in deionized water for 1 day, and allowed to stand in a fume hood for 24 h to obtain ionic liquid impregnated modified antibacterial nylon fiber.

[0101] Example 6

[0102] This embodiment provides a method for preparing an ionic liquid-impregnated modified antibacterial nylon fiber, comprising the following steps:

[0103] (1) dissolving m-phenylenediamine and 1-aminopropyl-3-methylimidazolium glycine salt (prepared in the laboratory, the preparation method refers to the prior art "Absorption of CO2 by Amino Acid Ionic Liquid-MDEA Composite Liquid" (Xia Peiwen, Wang Qiang, Zhang Pengjun, et al. Ion Exchange and Adsorption, 2019, 35(2): 123-130)) in water, stirring evenly at 25°C to obtain an ionic liquid antibacterial impregnation solution, wherein the concentration of m-phenylenediamine is 1wt% and the concentration of the ionic liquid is 1wt%;

[0104] (2) Weighing 5 g of nylon fiber, immersing it in a pre-prepared 648 mL, 0.2 wt % sodium dodecyl sulfate aqueous solution, ultrasonically cleaning it for 5 min, then ultrasonically cleaning it with ethanol for 10 min, and finally stirring and cleaning it with deionized water for 3 times, cleaning it for 10 min, and standing it in a fume hood for 24 h to dry, thereby obtaining pretreated nylon fiber;

[0105] (3) 5 g of pretreated nylon fiber was immersed in 1000 mL of ionic liquid antibacterial impregnation solution for 10 min at room temperature, and then vacuum dried in an oven at 100 °C for 10 min; then immersed in deionized water for 1 day, and allowed to stand in a fume hood for 24 h to obtain ionic liquid impregnated modified antibacterial nylon fiber.

[0106] Example 7

[0107] This embodiment provides a method for preparing an ionic liquid-impregnated modified antibacterial nylon fiber, comprising the following steps:

[0108] (1) dissolving m-phenylenediamine and bis-aminopropyl imidazole bis-trifluoromethanesulfonyl imine salt (purchased from Gaide Chemical Network) in water, stirring evenly at 25° C. to obtain an ionic liquid antibacterial impregnation solution, wherein the concentration of m-phenylenediamine is 1 wt % and the concentration of the ionic liquid is 1 wt %;

[0109] (2) Weighing 5 g of nylon fiber, immersing it in a pre-prepared 648 mL, 0.2 wt % sodium dodecyl sulfate aqueous solution, ultrasonically cleaning it for 5 min, then ultrasonically cleaning it with ethanol for 10 min, and finally stirring and cleaning it with deionized water for 3 times, cleaning it for 10 min, and standing it in a fume hood for 24 h to dry, thereby obtaining pretreated nylon fiber;

[0110] (3) 5 g of pretreated nylon fiber was immersed in 1000 mL of ionic liquid antibacterial impregnation solution for 10 min at room temperature, and then vacuum dried in an oven at 100 °C for 10 min; then immersed in deionized water for 1 day, and allowed to stand in a fume hood for 24 h to obtain ionic liquid impregnated modified antibacterial nylon fiber.

[0111] Test Example 1

[0112] The five nylon fibers obtained in Examples 1 to 7 and Comparative Example 1 were woven into non-woven fabrics, and then cut into discs with a diameter of 20 mm for antibacterial testing. The testing method is as follows:

[0113] In the clean bench, pour 25 mL of agar medium into sterile culture dishes and cool and solidify naturally. Use a pipette to take 1×10 8100 μL of CFU / mL Escherichia coli suspension was inoculated onto the culture medium and evenly spread on the surface of the agar culture medium with a smear stick; the five circular non-woven fabric samples with a diameter of 20 mm were placed on the center surface of the agar culture medium, covered with a culture dish lid, inverted, and cultured in an incubator at 37°C for 24 hours to observe the results.

[0114] Test Example 2

[0115] The clamping distance is set to 500mm, the stretching speed is 500mm / min constant speed stretching, and the breaking threshold is 50%. The specific test method is carried out in accordance with GB / T 14344-2008 "Test method for tensile properties of chemical fiber filaments", and the mechanical properties such as breaking strength, breaking elongation, initial modulus, etc. of the five nylon fiber single yarns obtained in Examples 1 to 7 and Comparative Example 1 are obtained. Each sample is tested 10 times and the average value is taken.

[0116] The results of test example 1 and test example 2 are shown in Table 1.

[0117] Table 1. Test results of nylon fibers obtained in Examples 1 to 7 and Comparative Example 1

[0118]

[0119]

[0120] The results in Table 1 show that the nylon fiber does not show an antibacterial zone in the culture dish containing two bacteria, Escherichia coli and Staphylococcus aureus, indicating that it itself does not have antibacterial properties. The nylon fiber impregnated with ionic liquid has antibacterial properties. Under the same conditions, the nylon fiber modified with 1-aminopropyl-3-methylimidazole alanine salt has a significant antibacterial effect, and with the increase of the ionic liquid concentration, the antibacterial effect shows a trend of increasing first and then decreasing. When the ionic liquid concentration is 1wt% (Example 2), the antibacterial zone of the antibacterial nylon fiber is the largest and the antibacterial effect is the most obvious. When the ionic liquid concentration increases from 0.5wt% to 1wt%, the chance of contact between the ionic liquid and the bacteria and the scope of leaching are increased, thereby improving the antibacterial effect of the nylon fiber; when the ionic liquid concentration increases from 1wt% to 2wt%, the antibacterial zone increases in an unobvious trend, but it also has an excellent antibacterial effect, indicating that the antibacterial nylon fiber is mainly antibacterial through the contact between the ionic liquid cation and the bacterial cell wall.

[0121] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing an ionic liquid impregnated modified antibacterial nylon fiber, characterized in that: The following steps are involved: (1) mixing an ionic liquid solubilizing agent, an ionic liquid and water to obtain an ionic liquid antibacterial impregnation solution; (2) immersing the nylon fiber in a surfactant solution for surface treatment to obtain pretreated nylon fiber; (3) impregnating the pretreated nylon fiber in step (2) with the ionic liquid antibacterial impregnation solution in step (1), and drying the impregnated nylon fiber to obtain the ionic liquid impregnated modified antibacterial nylon fiber; There is no order restriction for step (1) and step (2); The cation of the ionic liquid in step (1) includes an imidazolium cation, a quaternary ammonium salt cation, a guanidine cation or a quaternary phosphonium salt cation; The anion of the ionic liquid in step (1) comprises chloride ion, bromide ion, iodide ion, hydroxide ion, carbonate ion, bicarbonate ion, fluoroborate ion, hexafluorophosphate ion, bis(fluorosulfonyl)imide ion, bistrifluoromethanesulfonylimide ion, hexafluoroantimonate ion, bistrifluoromethanesulfonyl ion, acetate ion, lysine ion, glutamate ion, glycine ion or alanine ion; The imidazolium cation includes a di-substituted imidazolium cation, a ternary substituted imidazolium cation or a quaternary substituted imidazolium cation; The dibasic substituted imidazolium cation includes 1,3-dimethylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-allyl-3-methylimidazolium cation, 1-butyl-3-ethylimidazolium cation, 1-benzyl-3-methylimidazolium cation, 1-butyl-3-allylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-hexadecyl-3-methylimidazolium cation, 1-eicosyl-3-methylimidazolium cation, N-methylimidazolium cation, N-butylimidazolium cation, N-dodecylimidazolium cation, 1-aminoethyl-3-methylimidazolium cation, 1-aminopropyl-3-methylimidazolium cation, bisaminoethylimidazolium cation or bisaminopropylimidazolium cation; The ternary substituted imidazolium cation includes 1,2,3-trimethylimidazolium cation, 1,3,4-trimethylimidazolium cation, 1,3-dibutyl-2-methylimidazolium cation, 1-butyl-3,4-dimethylimidazolium cation, 1-dodecyl-3,4-dimethylimidazolium cation, 1-dodecyl-2,3-dimethylimidazolium cation, 1-butyl-3,4-dimethylimidazolium cation, 1-benzyl-3,4-dimethylimidazolium cation, 1-benzyl-2,3-dimethylimidazolium cation, 1-benzyl-3,4-dodecylimidazolium cation, 1-butyl-3,4-dipropylimidazolium cation, 1-dodecyl-3,4-dibutylimidazolium cation, 1-benzyl-3,4-hexadecylimidazolium cation or 1-benzyl-2,3-dibutylimidazolium cation; The quaternary substituted imidazolium cation includes 1,3,4,5-tetramethylimidazolium cation, 1,4,5-trimethyl-3-butylimidazolium cation, 1-methyl-3,4,5-tributylimidazolium cation, 1-methyl-3,4,5-trihexylimidazolium cation or 1-methyl-4,5-dibutyl-3-hexylimidazolium cation; The quaternary ammonium salt cations include N,N,N-tri(ethyl)methylammonium cations, N,N,N-tri(n-butyl)methylammonium cations, dodecyldimethylbenzylammonium cations, dodecyltrimethylammonium cations, tetradecyldimethylbenzylammonium cations, cyanoquaternary ammonium salt cations, di-C8 alkylquaternary ammonium cations, polynitrogen heterocyclic quaternary ammonium cations or monoaminated quaternary ammonium cations; The guanidine cations include long-chain alkylguanidine cations or biguanidine cations; The long-chain alkylguanidine cation includes a dodecylguanidine cation, an octaguanidine acetate cation, a biguanide cation or a polyhexamethyleneguanidine cation; The biguanide cation includes a polyhexamethylene biguanide cation or a polyaminopropyl biguanide cation; The quaternary phosphonium salt cations include triethyl (methyl) phosphonium cation, tri-n-butyl (methyl) phosphonium cation, tripropyl (methyl) phosphonium cation, tri-n-hexyl (methyl) phosphonium cation, tri-n-octyl (methyl) phosphonium cation, tri-n-dodecyl (methyl) phosphonium cation, dihexyl (ethyl) (methyl) phosphonium cation, di-n-butyl (ethyl) (methyl) phosphonium cation, tri-dodecyl (methyl) phosphonium cation, di-hexadecyl di-ethyl phosphonium cation, tetra-n-butyl phosphonium cation, tetra-n-hexyl phosphonium cation, tetra-hexadecyl phosphonium cation, tetra-dodecyl phosphonium cation, tri-dodecyl (ethyl) phosphonium cation or tri-dodecyl (n-butyl) phosphonium cation.

2. The preparation method according to claim 1, characterized in that: The ionic liquid solubilizing agent in step (1) includes piperazine or m-phenylenediamine; in the ionic liquid antibacterial impregnation solution in step (1), the mass concentration of the ionic liquid solubilizing agent is 0.3-1.5%, and the mass concentration of the ionic liquid is 0.5-3%.

3. The preparation method according to claim 1 or 2, characterized in that: The ionic liquid in step (1) includes 1-ethyl-3-methylimidazolium glycine salt, 1-aminopropyl-3-methylimidazolium glycine salt, 1-aminopropyl-3-methylimidazolium alanine salt, bis-aminoethyl imidazolium bis-trifluoromethanesulfonyl imide salt or bis-aminopropyl imidazolium bis-trifluoromethanesulfonyl imide salt.

4. The preparation method according to claim 1, characterized in that: In step (2), the surfactant in the surfactant solution includes sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate or sulfonated polyether, the mass concentration of the surfactant solution is 0.1-0.5%, and the mass-to-volume ratio of the nylon fiber to the surfactant solution is 5-15 mg:1 mL.

5. The preparation method according to claim 4, characterized in that: The surface treatment time in step (2) is 5 to 10 minutes.

6. The preparation method according to claim 1 or 4, characterized in that: In step (3), the mass-to-volume ratio of the pretreated nylon fiber to the ionic liquid antibacterial impregnation solution is 2-10 mg:1 mL.

7. The preparation method according to claim 6, characterized in that: The immersion treatment in step (3) is carried out at room temperature for 5 to 10 minutes.

8. The preparation method according to claim 1 or 7, characterized in that: In step (3), the drying temperature is 90 to 120° C. and the drying time is 5 to 20 minutes.

9. The antibacterial nylon fiber impregnated with ionic liquid prepared by the preparation method according to any one of claims 1 to 8.

Images