A modified spandex fabric and a preparation method thereof

Abstract

The application relates to the technical field of textiles, and discloses a modified spandex fabric and a preparation method thereof. Allyloxy butyric acid-based cyclodextrin is irradiated and grafted onto spandex fibers through ultraviolet irradiation grafting reaction to obtain butyric acid-based cyclodextrin grafted spandex fabric. Finally, quaternary ammonium tannic acid is included. The carboxyl groups of the cyclodextrin can have electrostatic interaction with the quaternary ammonium tannic acid, so that the inclusion of the cyclodextrin on the tannic acid is enhanced, the inclusion rate is improved, the loading capacity of the spandex fabric on the quaternary ammonium tannic acid is increased, the antibacterial performance of the spandex fabric is enhanced, and the spandex fabric still has long-acting antibacterial performance after being washed for many times.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of textiles, in particular to a modified spandex fabric and a preparation method thereof. BACKGROUND

[0002] In daily life, textiles such as clothes and towels are prone to bacterial growth in a high-temperature and humid environment, which has a great impact on health; in recent years, with the continuous improvement of living standards, people's health and safety awareness is also increasing, and antibacterial textiles have emerged as the times require; as a kind of elastic fiber, spandex has been widely used in clothing and fabric products, but traditional spandex fabric textiles do not have antibacterial properties and are prone to bacterial growth, so it is necessary to develop spandex fabric with antibacterial effect.

[0003] Beta-cyclodextrin has good biocompatibility, and its cavity structure has good specific inclusion effect on quaternary ammonium salt, natural compounds and various organic compounds, so that beta-cyclodextrin can be applied to the fields of antibacterial materials and textile finishing agents.

[0004] Tannic acid is a water-soluble polyphenol compound, which widely exists in various plants and has unique biological activity and strong antibacterial activity; a tannic acid containing a double quaternary ammonium salt structure is disclosed in Chinese Patent Application No. CN115677799A, which has the characteristics of significant bactericidal effect and wide application prospect in the food, packaging, feed and coating industries; the present application prepares a cyclodextrin grafted spandex fabric, which contains quaternary ammonium tannic acid, thereby improving the long-acting antibacterial performance of the spandex fabric. SUMMARY

[0005] The technical problem solved by the present application is to provide a modified spandex fabric and a preparation method thereof, which solves the problem of long-acting antibacterial performance of the spandex fabric.

[0006] The technical scheme of the present application is as follows:

[0007] A preparation method of a modified spandex fabric:

[0008] S1, adding N,N-dimethylformamide, mono-6-oxy-p-toluenesulfonyl cyclodextrin and allyloxybutyric acid into a flask, purging nitrogen into the flask, stirring and reacting, pouring the solution into methanol to precipitate, filtering, washing with ethanol and drying to obtain allyloxybutyric acid cyclodextrin.

[0009] S2, adding water, allyloxybutyric acid cyclodextrin and benzophenone into a reaction dish, stirring and dissolving, adding spandex fabric, irradiating under a UV lamp for 10-30 min, filtering, washing and drying to obtain butyric acid cyclodextrin grafted spandex fabric.

[0010] S3, water, quaternary ammonium tannic acid is added to the flask, stirring and dissolving, then adding butyric acid based cyclodextrin grafted spandex fabric, heating to 40-50 DEG C stirring 4-10h, filtration, washing, drying, to obtain modified spandex fabric.

[0011] Further, the ratio of N,N-dimethylformamide, mono-6-oxo-p-toluenesulfonyl cyclodextrin, allyloxy butyric acid in S1 is (10-20) mL:1g:(5-8)g.

[0012] Further, the reaction temperature in S1 is 75-90 DEG C, and the time is 48-96h.

[0013] Further, the ratio of water, allyloxy butyric acid based cyclodextrin, benzophenone in S2 is 1L:(10-50)g:(0.6-3)g.

[0014] Further, the ratio of water, quaternary ammonium tannic acid in S3 is 1L:(2-10)g.

[0015] Further, allyloxy butyric acid is prepared as follows: a flask is added with 1,4 dioxane, boc-4-amino-3-hydroxy butyric acid, bromine propylene and sodium hydride in a ratio of (15-25) mL:1g:(0.45-0.6)g:(0.2-0.3)g, heating to 60-80 DEG C stirring 3-6h, cooling, rotary evaporation to remove the solvent, washed with diethyl ether; the product is added to hydrogen chloride in ethyl acetate solution, stirring at room temperature for 2-3h, rotary evaporation to remove the solvent, washed with diethyl ether, drying, to obtain allyloxy butyric acid.

[0016] Further, quaternary ammonium tannic acid is prepared as follows: a flask is added with acetone, tannic acid, 2,3-epoxypropyl trimethyl ammonium chloride, sodium hydroxide and water in a ratio of (8-15) mL 1g:(0.3-0.8)g:(0.12-0.3)g:(8-15) mL, heating to 50-70 DEG C refluxing 4-8h, cooling, adding dilute hydrochloric acid dropwise for neutralization, rotary evaporation to remove the solvent, the product is recrystallized with ethanol, to obtain quaternary ammonium tannic acid.

[0017] The beneficial technical effects of the present application are: in the sodium hydroxide system, the epoxy group of 2,3-epoxypropyl trimethyl ammonium chloride and the hydroxyl group of tannic acid are used for ring opening reaction, to obtain quaternary ammonium tannic acid. Quaternary ammonium tannic acid contains bioactive polyphenol structure and antibacterial quaternary ammonium salt structure, and has high antibacterial performance.

[0018] In a sodium hydride catalytic system, boc-4-amino-3-hydroxybutyric acid and bromine propylene are reacted, and hydrochloric acid is used to remove the Boc protection to obtain allyloxy butyric acid, which is then reacted with mono-6-oxo-p-toluenesulfonyl cyclodextrin to obtain allyloxy butyric acid cyclodextrin, thereby realizing the introduction of an alkenyl group and a carboxyl group into β-cyclodextrin. The alkenyl group provides a grafting reaction site for β-cyclodextrin, and the carboxyl group can improve the hydrophilicity and water solubility of β-cyclodextrin, facilitating subsequent grafting reactions,

[0019] The allyloxy butyric acid cyclodextrin is used for irradiation grafting on spandex fibers by ultraviolet irradiation grafting reaction to obtain butyric acid cyclodextrin grafted spandex fabric. Finally, the quaternary ammonium tannic acid is included. The carboxyl group of cyclodextrin can interact with quaternary ammonium tannic acid through electrostatic interaction, thereby enhancing the inclusion of cyclodextrin on tannic acid, improving the inclusion rate, and increasing the loading capacity of spandex fabric on quaternary ammonium tannic acid, which is conducive to enhancing the antibacterial performance of spandex fabric. Moreover, after washing, the spandex fabric still has long-term antibacterial performance. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 is the preparation reaction formula of allyloxy butyric acid.

[0021] Figure 2 is the preparation reaction route of allyloxy butyric acid cyclodextrin. DETAILED DESCRIPTION

[0022] In order to more clearly illustrate the technical solutions of the present application, the following examples are listed. The raw materials, reactions and post-treatment methods appearing in the examples are all common raw materials on the market and technical means familiar to those skilled in the art, unless otherwise stated.

[0023] Mono-6-oxo-p-toluenesulfonyl cyclodextrin is prepared as follows: 10 g of β-cyclodextrin is added to a flask, 70 mL of water is added, and stirring is performed. Then, 30 mL of 1 mol / L NaOH solution is added, and p-toluenesulfonic acid chloride is added dropwise at 0℃. Stirring is performed for 3 h, and then the filtrate is filtered. Hydrochloric acid solution is added dropwise to adjust the pH to neutral, and a precipitate is separated out. The precipitate is filtered, and then added to wastewater. The insoluble matter is removed by hot filtration. The filtrate is allowed to stand at 0℃ for 12 h, and then filtered. The solid product is collected, and recrystallized from water to obtain mono-6-oxo-p-toluenesulfonyl cyclodextrin.

[0024] Example 1

[0025] (1) 50 mL of acetone, 5 g of tannic acid, 1.5 g of 2,3-epoxypropyl trimethyl ammonium chloride, 0.6 g of sodium hydroxide and 50 mL of water are added to a flask, and the temperature is raised to 60℃ for refluxing for 5 h. Cooling is performed, and dilute hydrochloric acid is added dropwise for neutralization. The solvent is removed by rotary evaporation, and the product is recrystallized from ethanol to obtain quaternary ammonium tannic acid.

[0026] (2) To the flask, 50 mL of 1,4 dioxane, 3 g of boc-4-amino-3-hydroxybutyric acid, 1.56 g of bromopropylene and 0.72 g of sodium hydride were added, and stirred at 70°C for 6 h, cooled, and the solvent was removed by rotary evaporation, washed with diethyl ether; the product was added to 50 mL of 4 mol / L hydrogen chloride in ethyl acetate solution, stirred at room temperature for 2 h, the solvent was removed by rotary evaporation, washed with diethyl ether, and dried to obtain allyloxybutyric acid.

[0027] (3) To the flask, 5 mL of N,N-dimethylformamide, 0.5 g of mono-6-oxy-p-toluenesulfonyl cyclodextrin, 3.2 g of allyloxybutyric acid were added, and nitrogen was introduced into the flask, and stirred at 80°C for 96 h, the solution was poured into methanol to precipitate the product, suction filtered, washed with ethanol, and dried to obtain allyloxybutyric acid cyclodextrin.

[0028] (4) To the reaction dish, 50 mL of water, 0.5 g of allyloxybutyric acid cyclodextrin, 0.03 g of benzophenone were added, stirred and dissolved, and spandex fabric was added, and irradiated under a UV lamp with a power of 80 W for 20 min, filtered, washed, and dried to obtain butyric acid cyclodextrin grafted spandex fabric.

[0029] (5) To the flask, 1 L of water, 2 g of quaternary ammonium tannic acid were added, stirred and dissolved, and then butyric acid cyclodextrin grafted spandex fabric was added, and stirred at 50°C for 8 h, filtered, washed with water, and dried to obtain modified spandex fabric.

[0030] Example 2 differs from Example 1 in that: (1) To the flask, 50 mL of acetone, 5 g of tannic acid, 3 g of 2,3-epoxypropyltrimethylammonium chloride, 1.1 g of sodium hydroxide and 50 mL of water were added, and stirred at 60°C for 5 h, cooled, and neutralized by adding dilute hydrochloric acid dropwise, the solvent was removed by rotary evaporation, and the product was recrystallized with ethanol to obtain quaternary ammonium tannic acid.

[0031] Example 3 differs from Example 1 in that: (1) To the flask, 75 mL of acetone, 5 g of tannic acid, 4 g of 2,3-epoxypropyltrimethylammonium chloride, 1.5 g of sodium hydroxide and 75 mL of water were added, and stirred at 60°C for 5 h, cooled, and neutralized by adding dilute hydrochloric acid dropwise, the solvent was removed by rotary evaporation, and the product was recrystallized with ethanol to obtain quaternary ammonium tannic acid.

[0032] Example 4 differs from Example 2 in that: (4) To the reaction dish, 50 mL of water, 1 g of allyloxybutyric acid cyclodextrin, 0.06 g of benzophenone were added, stirred and dissolved, and spandex fabric was added, and irradiated under a UV lamp with a power of 80 W for 20 min, filtered, washed, and dried to obtain butyric acid cyclodextrin grafted spandex fabric.

[0033] Example 5 differs from Example 2 in that: (4) 50 mL of water, 1.8 g of allyloxy butyric acid cyclodextrin, 0.1 g of benzophenone were added to the reaction dish, stirred and dissolved, the spandex fabric was added, and irradiated under a UV lamp with a power of 80 W for 20 min, filtered, washed, and dried to obtain the butyric acid cyclodextrin grafted spandex fabric.

[0034] Example 6 differs from Example 2 in that: (4) 50 mL of water, 2.5 g of allyloxy butyric acid cyclodextrin, 0.15 g of benzophenone were added to the reaction dish, stirred and dissolved, the spandex fabric was added, and irradiated under a UV lamp with a power of 80 W for 20 min, filtered, washed, and dried to obtain the butyric acid cyclodextrin grafted spandex fabric.

[0035] Example 7 differs from Example 6 in that: (5) 1 L of water, 4 g of quaternary ammonium tannic acid were added to the flask, stirred and dissolved, and then the butyric acid cyclodextrin grafted spandex fabric was added, and stirred at 50°C for 8 h, filtered, washed with water, and dried to obtain the modified spandex fabric.

[0036] Example 8 differs from Example 6 in that: (5) 1 L of water, 6 g of quaternary ammonium tannic acid were added to the flask, stirred and dissolved, and then the butyric acid cyclodextrin grafted spandex fabric was added, and stirred at 50°C for 8 h, filtered, washed with water, and dried to obtain the modified spandex fabric.

[0037] Example 9 differs from Example 6 in that: (5) 1 L of water, 8 g of quaternary ammonium tannic acid were added to the flask, stirred and dissolved, and then the butyric acid cyclodextrin grafted spandex fabric was added, and stirred at 50°C for 8 h, filtered, washed with water, and dried to obtain the modified spandex fabric.

[0038] Example 10 differs from Example 6 in that: (5) 1 L of water, 10 g of quaternary ammonium tannic acid were added to the flask, stirred and dissolved, and then the butyric acid cyclodextrin grafted spandex fabric was added, and stirred at 50°C for 8 h, filtered, washed with water, and dried to obtain the modified spandex fabric.

[0039] Comparative Example 1 differs from Example 1 in that: (5) 1 L of water, 2 g of tannic acid were added to the flask, stirred and dissolved, and then the butyric acid cyclodextrin grafted spandex fabric was added, and stirred at 50°C for 8 h, filtered, washed with water, and dried to obtain the modified spandex fabric.

[0040] Comparative Example 2 differs from Example 1 in that: (5) 1 L of water, 2 g of 2,3-epoxypropyl trimethyl ammonium chloride were added to the flask, stirred and dissolved, and then the butyric acid cyclodextrin grafted spandex fabric was added, and stirred at 50°C for 8 h, filtered, washed with water, and dried to obtain the modified spandex fabric.

[0041] Antibacterial test: The antibacterial performance of the modified spandex fabric against E. coli was tested according to GB / T 20944.1-2007 "Evaluation of antibacterial properties of textiles - Part 1: Agar plate diffusion method" and GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Shake flask method".

[0042] Washing resistance test: The modified spandex fabric prepared in Example 9 was subjected to water washing test according to GB / T 8629-2001 "Home laundry and drying procedures for testing textiles", and the number of washing was 10, 30 and 50 times, respectively. Then the antibacterial test was performed.

[0043] Table 1 Antibacterial test I

[0044] Bacteriostatic rate (%) Example 1 62.4 Example 2 74.2 Example 3 73.5 Comparative Example 1 32.1 Comparative Example 2 50.6 Comparative Example 3 6.5

[0045] Comparative Example 3 is the butyric acid-based cyclodextrin grafted spandex fabric prepared in step (4) of Example 1.

[0046] As can be seen from Examples 1-3, when the ratio of tannic acid (5 g) to 2,3-epoxypropyltrimethylammonium chloride (3 g) is 1:0.6, the quaternary ammonium tannic acid obtained is included in the modified spandex fabric, and the fabric has better antibacterial performance against E. coli. With the increase of the amount of 2,3-epoxypropyltrimethylammonium chloride, the antibacterial rate of the fabric has a slight downward trend.

[0047] In Comparative Example 1, the butyric acid-based cyclodextrin grafted spandex fabric is included with tannic acid, and Comparative Example 1 is included with 2,3-epoxypropyltrimethylammonium chloride, and the antibacterial rate of both is less than that of Example 1.

[0048] Table 2 Antibacterial test II

[0049] Bacteriostatic rate (%) Example 2 74.2 Example 4 82.4 Example 5 92.6 Example 6 93.3

[0050] As can be seen from Examples 2, 4-6, during the ultraviolet light grafting process, when the mass fraction of allyloxy butyric acid-based cyclodextrin in the solution is 36 g / L, the antibacterial rate of the modified spandex fabric against E. coli reaches 92.6%; when the mass fraction is 50 g / L, the antibacterial rate of the modified spandex fabric has a small increase, reaching 93.3%.

[0051] Table 3 Antibacterial test III

[0052] Bacteriostatic rate (%) Example 6 93.3 Example 7 97.3 Example 8 99.2 Example 9 99.9 Example 10 99.9

[0053] As can be seen from Examples 6-9, when the butyric acid-based cyclodextrin grafted spandex fabric is used to include the quaternary ammonium tannic acid, the antibacterial rate of the fabric is 99.2% when the mass fraction of the quaternary ammonium tannic acid in the solution is 6 g / L, and the antibacterial rate reaches 99.9% when the mass fraction is 8-10 g / L. It is possible that the inclusion amount of the butyric acid-based cyclodextrin grafted spandex fabric to the quaternary ammonium tannic acid reaches saturation when the mass fraction is 8 g / L.

[0054] Table 4 antibacterial performance test four

[0055]

[0056] After 50 times of washing, the antibacterial rate is still 92.0%.

[0057] The present application also has other various embodiments, and those skilled in the art can make various corresponding changes and modifications according to the present application without departing from the spirit and essence of the present application. However, these corresponding changes and modifications should all belong to the protection scope of the present application.

Claims

1. A method for preparing a modified spandex fabric, characterized by, The modified spandex fabric is prepared by the following method: S1, adding N,N-dimethylformamide, mono-6-oxy-p-toluenesulfonyl cyclodextrin, allyloxy butyric acid into a flask, purging nitrogen, stirring and reacting, pouring the solution into methanol to precipitate, filtering, washing, drying, and obtaining allyloxy butyric acid cyclodextrin; S2, adding water, allyloxy butyric acid cyclodextrin, and benzophenone into a reaction dish, stirring and dissolving, adding spandex fabric, irradiating under ultraviolet lamp for 10-30 min, filtering, washing, and drying to obtain butyric acid cyclodextrin grafted spandex fabric; S3, adding water and quaternary ammonium tannic acid into a flask, stirring and dissolving, then adding butyric acid cyclodextrin grafted spandex fabric, heating to 40-50℃ and stirring for 4-10 h, filtering, washing, and drying to obtain modified spandex fabric; The reaction temperature in S1 is 75-90℃, and the time is 48-96 h; The ratio of water, allyloxy butyric acid cyclodextrin, and benzophenone in S2 is 1L:(36-50)g:(2-3)g; The ratio of water and quaternary ammonium tannic acid in S3 is 1L:(2-10)g; The allyloxy butyric acid is prepared by the following method: adding 1,4 dioxane, boc-4-amino-3-hydroxy butyric acid, bromine propylene, and sodium hydride into a flask, heating to 60-80℃ and stirring for 3-6 h, cooling, removing the solvent by rotary evaporation, washing; adding the product into a hydrogen chloride ethyl acetate solution, stirring at room temperature for 2-3 h, removing the solvent by rotary evaporation, washing, and drying to obtain allyloxy butyric acid; The quaternary ammonium tannic acid is prepared by the following method: adding acetone, tannic acid, 2,3-epoxypropyl trimethyl ammonium chloride, sodium hydroxide, and water into a flask, heating to 50-70℃ and refluxing for 4-8 h, cooling, adding dilute hydrochloric acid dropwise for neutralization, rotary evaporation, and recrystallization to obtain quaternary ammonium tannic acid; The ratio of acetone, tannic acid, 2,3-epoxypropyl trimethyl ammonium chloride, sodium hydroxide, and water is (10-15)mL:1g:(0.6-0.8)g:(0.22-0.3)g:(10-15)mL.

2. The method of claim 1, wherein the modified spandex fabric is prepared by the steps of: The ratio of N,N-dimethylformamide, mono-6-oxy-p-toluenesulfonyl cyclodextrin, and allyloxy butyric acid in S1 is (10-20)mL:1g:(5-8)g.

3. The method for preparing modified spandex fabric according to claim 1, characterized in that, The ratio of 1,4 dioxane, boc-4-amino-3-hydroxy butyric acid, bromine propylene, and sodium hydride is (15-25)mL:1g:(0.45-0.6)g:(0.2-0.3)g.

Images