阅读说明：本技术 一种锦纶纤维的制备方法 (Preparation method of nylon fiber ) 是由 廖国庆 于 2020-07-06 设计创作，主要内容包括：本发明公开了一种锦纶纤维的制备方法,包括如下步骤：(1)锦纶切片熔融后经喷丝板喷丝,冷却后得到单丝；(2)用含有表面改性介孔纳米TiO<Sub>2</Sub>的改性浆料对单丝进行喷涂改性；(3)喷涂改性后的单丝集束上油后进入甬道纺丝；(4)拉伸、卷绕后得到所述锦纶纤维。本发明在锦纶纤维制备过程中使用含有表面改性的介孔纳米TiO<Sub>2</Sub>的浆料对纤维进行喷涂改性,使纳米TiO<Sub>2</Sub>均匀分布在锦纶纤维中,随纤维纺织成织物后可以使织物同时具有良好的抗老化性能和透气性,同时通过表面改性抑制了纳米TiO<Sub>2</Sub>的光催化活性,提高了锦纶纤维的抗老化性能。(The invention discloses a preparation method of nylon fiber, which comprises the following steps: (1) melting the nylon chips, spraying yarns by a spinneret plate, and cooling to obtain monofilaments; (2) using mesoporous nano TiO containing surface modification 2 The monofilament is sprayed and modified by the modified sizing agent; (3) spraying modified monofilament bundles, oiling, and then entering channel spinning; (4) and stretching and winding to obtain the nylon fiber. The invention uses mesoporous nanometer TiO containing surface modification in the preparation process of the nylon fiber 2 The slurry is used for spraying and modifying the fiber to ensure that the nano TiO 2 The nano TiO nano composite material is uniformly distributed in the nylon fiber, can enable the fabric to have good ageing resistance and air permeability after being spun into the fabric along with the fiber, and simultaneously inhibits the nano TiO through surface modification 2 The photocatalytic activity of the polyamide fiber is improved, and the anti-aging performance of the polyamide fiber is improved.)

1. The preparation method of the nylon fiber is characterized by comprising the following steps:

(1) melting the nylon chips, spraying yarns by a spinneret plate, and cooling to obtain monofilaments;

(2) using mesoporous nano TiO containing surface modification₂The monofilament is sprayed and modified by the modified sizing agent;

(3) spraying modified monofilament bundles, oiling, and then entering channel spinning;

(4) and stretching and winding to obtain the nylon fiber.

2. The method for preparing nylon fiber according to claim 1, wherein the modified slurry in step (2) comprises surface-modified mesoporous nano TiO₂And polyacrylate emulsion, surface modified mesoporous nano TiO₂The mass fraction of the modified slurry is 10-30%.

3. The preparation method of nylon fiber according to claim 1 or 2, wherein the spraying quality of the modified slurry in the step (2) is 5-10% of the conveying capacity of the nylon chip melt in the step (1) in unit time.

4. The method for preparing nylon fiber according to claim 1, wherein the temperature in the shaft in step (3) is 80-100 ℃.

5. The method for preparing nylon fiber according to claim 1 or 2, wherein the surface-modified mesoporous nano-fibers in step (2)TiO₂The preparation method comprises the following steps:

(a) dissolving hexadecylamine in absolute ethyl alcohol at 25-30 ℃, adding a potassium chloride solution and deionized water, and uniformly stirring to obtain a guiding agent solution;

(b) dropwise adding titanium isopropoxide into the guiding agent solution under the stirring state, standing for 15-24 h, centrifuging, washing the product with ethanol, and drying to obtain TiO₂The molar ratio of the added titanium isopropoxide to the hexadecylamine in the guiding agent solution is 1: (0.1 to 0.5);

(c) adding TiO into the mixture₂Dispersing the precursor in a mixed solution of ammonia water, absolute ethyl alcohol and deionized water, reacting at 150-180 ℃ for 12-24 h, centrifuging, washing the product with ethanol, drying, and roasting at 500-510 ℃ for 2-3 h to obtain mesoporous TiO₂；

(d) Downward mesoporous TiO under the protection of nitrogen₂Adding toluene, gamma-chloropropyltrimethoxysilane and 3-glycidyl ether oxypropyltriethoxysilane, stirring at 80-120 ℃ and reacting for 20-30 h to obtain surface-modified mesoporous TiO₂Mesoporous TiO₂The mass volume ratio of the mixture to toluene, gamma-chloropropyltrimethoxysilane and 3-glycidyl ether oxypropyltriethoxysilane is 1 g: (20-30 mL): (20-30 mL): (400-600 mL);

(e) adding alanine into phosphate buffer solution with pH of 7.0, stirring uniformly, and adding surface modified mesoporous TiO₂Oscillating and reacting for 20-30 h at 50-60 ℃, filtering, washing the product with ethanol, and drying in vacuum to obtain alanine-modified mesoporous TiO₂；

(f) Alanine modified mesoporous TiO₂Dispersing in an aromatic bacteriostatic agent, stirring at room temperature for reaction for 8-12 h, filtering, and washing with deionized water to obtain the aromatic bacteriostatic agent-loaded mesoporous TiO₂The alanine-modified mesoporous TiO₂The mass volume ratio of the aromatic bacteriostatic agent to the aromatic bacteriostatic agent is 1 g: (20-50 mL);

(g) loading mesoporous TiO with aromatic bacteriostat₂Dispersing in N, N-dimethylformamide, stirring for 30-40 min, adding octadecyl dimethyl tertiary amine and potassium iodide under the protection of nitrogen, stirring at 40-60 ℃ for reaction for 24-36 h, filtering, and mixingWashing the product with N, N-dimethylformamide, and drying in vacuum to obtain the surface modified mesoporous nano TiO₂。

6. The preparation method of nylon fiber according to claim 5, wherein the concentration of the potassium chloride solution in the step (a) is 0.1-0.2 mol/L, and the mass-to-volume ratio of the hexadecylamine to the added absolute ethyl alcohol, the potassium chloride solution and the deionized water is 1 g: (80-120 mL): (0.3-0.5 mL): (1-2 mL).

7. A preparation method of polyamide fiber according to claim 5, characterized in that the concentration of ammonia water in the mixed solution in step (c) is 0.1-0.2 mol/L, and the volume ratio of the absolute ethyl alcohol to the deionized water is (1-2): 1; TiO 2₂The mass volume ratio of the precursor to the mixed solution is 1 g: (18-22 mL).

8. The method for preparing nylon fiber according to claim 5, wherein the concentration of alanine in phosphate buffer solution in step (e) is 2-4 mg/mL, and surface-modified mesoporous TiO is added₂The mass volume ratio of the phosphate buffer solution to the phosphate buffer solution is 1 g: (100-200 mL).

9. The method for preparing nylon fiber according to claim 5, wherein the aromatic bacteriostatic agent in step (f) is one or more of rose essential oil, lemon essential oil, mint essential oil and blumea oil.

10. The method for preparing nylon fiber according to claim 5, wherein the mesoporous TiO loaded with aromatic bacteriostatic agent in step (g)₂The mass-to-volume ratio of N, N-dimethylformamide is 1 g: (200-400 mL) of mesoporous TiO loaded with aromatic bacteriostatic agent₂The mass ratio of the organic solvent to the octadecyl dimethyl tertiary amine and the potassium iodide is 5: (9-11): (0.1-0.5).

Technical Field

The invention relates to the technical field of functional fiber processing, in particular to a preparation method of nylon fiber.

Background

The nylon fiber is widely used in various textiles for clothing and industry, but the nylon fiber is easy to age in the using and storing process, so that the strength of the fiber is reduced, and the using performance is influenced. Light is a main factor influencing the ageing of nylon, and can accelerate the breakage of C-C bonds in nylon so as to accelerate the ageing degradation of the nylon, so that the ageing resistance of the nylon fabric is improved by finishing an ultraviolet-proof coating on the surface of the nylon fabric in the prior art.

However, when the coating is coated on the surface of the fabric, the air permeability of the fabric can be reduced, and the wearing comfort of the nylon fabric is influenced; the anti-ultraviolet active ingredient in the coating is usually nano titanium dioxide, and the nano titanium dioxide can absorb and reflect ultraviolet rays, but has certain photocatalytic activity and can catalyze the ageing degradation of nylon, so that the anti-aging capability of the nylon fabric is not improved.

Disclosure of Invention

The invention provides a preparation method of nylon fiber, aiming at overcoming the problems that in the prior art, when the anti-aging capability of nylon fabric is improved by finishing an ultraviolet-proof coating on the surface of the nylon fabric, the coating can reduce the air permeability of the nylon fabric, and the nano titanium dioxide in the coating has photocatalytic activity and can catalyze the aging degradation of nylon at the same time, which is not beneficial to improving the anti-aging capability of the nylon fabric, and the preparation method of the nylon fiber is provided₂The slurry is used for spraying and modifying the fiber to ensure that the nano TiO₂The nano TiO nano composite material is uniformly distributed in the nylon fiber, can enable the fabric to have good ageing resistance and air permeability after being spun into the fabric along with the fiber, and simultaneously inhibits the nano TiO through surface modification₂The photocatalytic activity of the polyamide fiber is improved, and the anti-aging performance of the polyamide fiber is improved.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of nylon fiber comprises the following steps:

(1) melting the nylon chips, spraying yarns by a spinneret plate, and cooling to obtain monofilaments;

(2) using mesoporous nano TiO containing surface modification₂The monofilament is sprayed and modified by the modified sizing agent;

(3) spraying modified monofilament bundles, oiling, and then entering channel spinning;

(4) and stretching and winding to obtain the nylon fiber.

Before the cluster spinning, the mesoporous nano TiO containing surface modification is used₂The modified sizing agent is used for spraying and modifying the monofilamentTo modify the surface of the mesoporous nano TiO₂Attached to the monofilament, then the sprayed monofilament is subjected to cluster oiling, spinning, stretching and winding to finally obtain the nylon fiber, so that the surface of the nylon fiber is modified with the mesoporous nano TiO₂Can be uniformly distributed in the nylon fiber. Surface modified mesoporous nano TiO₂The ultraviolet rays can be effectively absorbed and reflected, and the light-accelerated ageing of the polyamide fibers is avoided; nano TiO 2₂The photocatalytic activity of the mesoporous nano TiO is related to the reactive active sites on the surface, and the mesoporous nano TiO is prepared by the method₂Surface modification is carried out to seal the nano TiO₂The surface active site of (2) inhibits the nano TiO₂The photocatalytic performance of the nano TiO is avoided₂The anti-aging performance of the nylon fiber is further improved by reflecting and absorbing ultraviolet rays and simultaneously carrying out photocatalysis and ageing degradation on the nylon fiber.

Meanwhile, the surface modified mesoporous nano TiO is uniformly distributed in the nylon fiber₂After the nylon fibers are woven into nylon textiles, the air permeability of the textiles can not be influenced, and the influence of the traditional coating after-finishing method on the wearing comfort of the nylon textiles is avoided; also avoids directly mixing the nano TiO₂The nylon fiber is added into the nylon slice melt for common spinning to cause the problems of poor spinnability and easy breakage of the nylon fiber, and the prepared nylon textile has good ageing resistance and air permeability and good wearability.

Preferably, the modified slurry in the step (2) comprises surface modified mesoporous nano TiO₂And polyacrylate emulsion, surface modified mesoporous nano TiO₂The mass fraction of the modified slurry is 10-30%.

Preferably, the spraying quality of the modified slurry in the step (2) is 5-10% of the conveying capacity of the nylon chip melt in the step (1) per unit time.

Preferably, the temperature in the shaft in the step (3) is 80-100 ℃.

Preferably, the surface modified mesoporous nano TiO in the step (2)₂The preparation method comprises the following steps:

(a) dissolving hexadecylamine in absolute ethyl alcohol at 25-30 ℃, adding a potassium chloride solution and deionized water, and uniformly stirring to obtain a guiding agent solution;

(b) dropwise adding titanium isopropoxide into the guiding agent solution under the stirring state, standing for 15-24 h, centrifuging, washing the product with ethanol, and drying to obtain TiO₂The molar ratio of the added titanium isopropoxide to the hexadecylamine in the guiding agent solution is 1: (0.1 to 0.5);

(c) adding TiO into the mixture₂Dispersing the precursor in a mixed solution of ammonia water, absolute ethyl alcohol and deionized water, reacting at 150-180 ℃ for 12-24 h, centrifuging, washing the product with ethanol, drying, and roasting at 500-510 ℃ for 2-3 h to obtain mesoporous TiO₂；

(d) Downward mesoporous TiO under the protection of nitrogen₂Adding toluene, gamma-chloropropyltrimethoxysilane and 3-glycidyl ether oxypropyltriethoxysilane, stirring at 80-120 ℃ and reacting for 20-30 h to obtain surface-modified mesoporous TiO₂Mesoporous TiO₂The mass volume ratio of the mixture to toluene, gamma-chloropropyltrimethoxysilane and 3-glycidyl ether oxypropyltriethoxysilane is 1 g: (20-30 mL): (20-30 mL): (400-600 mL);

(e) adding alanine into phosphate buffer solution with pH of 7.0, stirring uniformly, and adding surface modified mesoporous TiO₂Oscillating and reacting for 20-30 h at 50-60 ℃, filtering, washing the product with ethanol, and drying in vacuum to obtain alanine-modified mesoporous TiO₂；

(f) Alanine modified mesoporous TiO₂Dispersing in an aromatic bacteriostatic agent, stirring at room temperature for reaction for 8-12 h, filtering, and washing with deionized water to obtain the aromatic bacteriostatic agent-loaded mesoporous TiO₂The alanine-modified mesoporous TiO₂The mass volume ratio of the aromatic bacteriostatic agent to the aromatic bacteriostatic agent is 1 g: (20-50 mL);

(g) loading mesoporous TiO with aromatic bacteriostat₂Dispersing in N, N-dimethylformamide, stirring for 30-40 min, adding octadecyl dimethyl tertiary amine and potassium iodide under the protection of nitrogen, stirring at 40-60 ℃ for reaction for 24-36 h, filtering, washing the product with N, N-dimethylformamide, and vacuum drying to obtain the surface modified mesoporous nano TiO₂。

The invention is in pairNano TiO 2₂In the process of surface modification, mesoporous TiO is prepared first₂Making TiO into₂Has good adsorption performance while having the function of ultraviolet resistance, thereby being capable of adsorbing in mesoporous TiO₂Aromatic bacteriostatic agent is loaded in the pore canal to ensure that the mesoporous TiO is₂Meanwhile, the aromatic bacteriostatic agent can be used as a carrier of the ultraviolet-proof agent and the aromatic bacteriostatic agent, so that the nylon fiber can release the aromatic bacteriostatic agent while preventing the nylon fiber from aging, and has the functions of fragrance release and deodorization.

The invention also relates to mesoporous TiO₂Alanine and long carbon chain quaternary ammonium salt are modified on the surface, and reaction between groups is utilized to react with mesoporous nano TiO₂Active sites on the surface are sealed, and mesoporous nano TiO is avoided₂The anti-aging performance of the nylon fiber is influenced by the degradation of the photocatalytic nylon fiber. And because the quaternary ammonium group in the long carbon chain quaternary ammonium salt is positively charged, and the isoelectric point of alanine is 6.02, the alanine is negatively charged under neutral and alkaline conditions, is attracted with the quaternary ammonium salt group, and the long carbon chain is covered on the mesoporous TiO under the attraction action₂The pore structure is closed, and the aromatic bacteriostatic agent loaded in the pore cannot be released; under the acidic condition that the pH value is less than 6.02, alanine is positively charged and is repelled with quaternary ammonium salt groups, and long carbon chains leave the mesoporous TiO under the repelling action₂The surface is unfolded, the pore structure is opened, and the aromatic bacteriostatic agent loaded in the pore can be released. Due to mesoporous TiO₂The closing and opening of the pore structure can be controlled along with the change of pH, so that the release of the loaded aromatic bacteriostatic agent can also be controlled by the external pH.

In the preparation process, firstly, the mesoporous TiO is prepared by the steps (a) to (c) and the hexadecylamine is used as a guiding agent₂Then, through the step (d), gamma-chloropropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are utilized to prepare the mesoporous TiO₂Modifying the surface with chloropropyl and epoxy; then, through the step (e), the epoxy group is utilized to open loop and graft alanine on the mesoporous TiO₂Introducing alanine on the surface; then loading the aromatic bacteriostatic agent in the mesoporous TiO through the step (f)₂In the duct of (2); finally, the step (g) of utilizing the mesoporous TiO under the reaction condition of neutral condition₂The surface gamma-chloropropyltrimethoxysilane and octadecyl dimethyl tertiary amine are subjected to quaternization reaction, and long carbon chain quaternary ammonium salt is introduced into the mesoporous TiO₂And (3) sealing the pore channel on the surface.

The sweat of human body is generally weakly acidic, the pH value is about 5.5, and the surface modified mesoporous nano TiO prepared by the method is distributed₂When the nylon fiber is woven into nylon fabric and worn on a human body, when sweat is generated on the human body, the sweat can be quickly absorbed due to good water absorption of the nylon fiber, so that the surface modified mesoporous nano TiO can₂Under the acidic condition, the pore channel structure is opened, and the mesoporous nano TiO is modified on the surface₂The aromatic bacteriostatic agent loaded in the sweat absorbent can be slowly released to kill bacteria on the skin, so that the bacteria are prevented from decomposing organic matters in sweat to generate peculiar smell, and the peculiar smell can be covered by the fragrance of the aromatic bacteriostatic agent, so that the deodorizing effect is achieved. After the fabric stained with sweat is cleaned, the surface of the fabric is modified with the mesoporous nano TiO under the washing action of neutral water₂The pore structure in the porous membrane is closed again, and the aromatic bacteriostatic agent stops releasing. Therefore, the aromatic bacteriostatic agent can not be released to cause loss when the fabric made of the nylon fiber is placed, and the aromatic bacteriostatic agent can be released to eliminate peculiar smell only when the fabric is worn on a human body and is in contact with sweat, so that the fragrance releasing durability is good.

Preferably, the concentration of the potassium chloride solution in the step (a) is 0.1-0.2 mol/L, and the mass-to-volume ratio of the hexadecylamine to the added absolute ethyl alcohol, the potassium chloride solution and the deionized water is 1 g: (80-120 mL): (0.3-0.5 mL): (1-2 mL).

Preferably, the concentration of ammonia water in the mixed solution in the step (c) is 0.1-0.2 mol/L, and the volume ratio of the absolute ethyl alcohol to the deionized water is (1-2): 1; TiO 2₂The mass volume ratio of the precursor to the mixed solution is 1 g: (18-22 mL).

Preferably, the concentration of alanine in the phosphate buffer solution in the step (e) is 2-4 mg/mL, and the surface modified mesoporous TiO is added₂The mass volume ratio of the phosphate buffer solution to the phosphate buffer solution is 1 g: (100-200 mL).

Preferably, the aromatic bacteriostatic agent in the step (f) is one or more of rose essential oil, lemon essential oil, mint essential oil and argy wormwood oil.

Preferably, the mesoporous TiO loaded with the aromatic bacteriostatic agent in the step (g)₂The mass-to-volume ratio of N, N-dimethylformamide is 1 g: (200-400 mL) of mesoporous TiO loaded with aromatic bacteriostatic agent₂The mass ratio of the organic solvent to the octadecyl dimethyl tertiary amine and the potassium iodide is 5: (9-11): (0.1-0.5).

Therefore, the invention has the following beneficial effects:

(1) in the preparation process of the nylon fiber, surface modified mesoporous nano TiO is used before cluster spinning₂The modified sizing agent is used for spraying and modifying the monofilament so as to lead the surface to be modified with mesoporous nano TiO₂The anti-aging nylon fiber is uniformly distributed in the prepared nylon fiber, so that the nylon fiber has good anti-aging performance and can be made into textiles without influencing the air permeability of the textiles;

(2) to mesoporous nano TiO₂Surface modification is carried out to seal the nano TiO₂The surface active site of (2) inhibits the nano TiO₂The photocatalytic performance of the nano TiO is avoided₂The ageing resistance of the nylon fiber is further improved by aging and degrading the photocatalytic nylon fiber;

(3) mesoporous nano TiO modified on surface₂The aromatic bacteriostatic agent is loaded in the nylon fabric and has a pH response slow-release function under the electrostatic action of the surface modification group, so that the aromatic bacteriostatic agent is not released when the nylon fiber is placed, and the aromatic bacteriostatic agent is released to eliminate peculiar smell only when the nylon fiber is worn on a human body and sweats, and the fragrance release duration is good.

Detailed Description

The invention is further described with reference to specific embodiments.

The reagents used in the present invention are as follows:

nylon-66 slicing: jiangsu Haiyang chemical fiber Co., Ltd;

spinning oil agent: shanghai Ice New Material science and technology, Inc.;

polyacrylate emulsion: the solid content is 40 percent, Shanghai Jiehun new material company;

rose essential oil: purity is more than or equal to 99 percent, Shanghai Zhengnzhen nanometer science and technology Limited company;

lemon essential oil: purity is more than or equal to 99 percent, Shanghai Zhengnzhi nano science and technology Limited company.

Other reagents used in the present invention are those commonly used in the art or commercially available.