Modified spandex fabric and preparation method thereof

Abstract

The invention relates to the technical field of textiles, and discloses a modified spandex fabric and a preparation method thereof.Ultraviolet light irradiation grafting reaction is adopted, spandex fibers are subjected to irradiation grafting through allyloxy butyric acid cyclodextrin to obtain butyric acid cyclodextrin grafted spandex fabric, and finally quaternized tannic acid is included to obtain the modified spandex fabric. The carboxyl of cyclodextrin can generate electrostatic interaction with quaternized tannic acid, so that the clathration effect of cyclodextrin on tannic acid is enhanced, the clathration rate is increased, the loading capacity of the spandex fabric on quaternized tannic acid is increased, the antibacterial property of the spandex fabric is enhanced, and the antibacterial property of the spandex fabric is improved after the spandex fabric is washed by much water. And the spandex fabric still has long-acting antibacterial performance.

Description

Technical Field

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

[0002] In daily life, clothing, towels and other textiles are prone to breed bacteria in hot and humid environments, which has a great impact on physical health. In recent years, with the continuous improvement of living standards, people's awareness of health and safety has become increasingly greater, and antibacterial textiles have emerged. Spandex, as an elastic fiber, has been widely used in clothing and fabric products, but traditional spandex fabric textiles do not have antibacterial properties and are prone to breed bacteria. Therefore, it is necessary to develop spandex fabrics with antibacterial effects.

[0003] β-cyclodextrin has good biocompatibility, and its cavity structure has good specific inclusion effect on various organic compounds such as quaternary ammonium salts and natural compounds, so that β-cyclodextrin can be used in the fields of antibacterial materials, textile finishing agents, etc.

[0004] Tannic acid is a water-soluble polyphenol compound, which is widely present in many plants, has unique biological activity, and can show strong antibacterial activity. The Chinese patent application with publication number CN115677799A discloses a tannic acid containing a diquaternary ammonium salt structure, which has the characteristics of significant bactericidal effect and has broad application prospects in the food, packaging, feed, coating and other industries. The present invention prepares a cyclodextrin grafted spandex fabric, contains quaternary ammonium tannic acid, and improves the long-term antibacterial performance of the spandex fabric. Summary of the invention

[0005] The technical problem solved by the present invention is: to provide a modified spandex fabric and a preparation method thereof, thereby solving the problem that the spandex fabric does not have long-lasting antibacterial performance.

[0006] The technical solution of the present invention is:

[0007] A method for preparing modified spandex fabric:

[0008] S1. Add N,N-dimethylformamide, mono-6-oxy-toluenesulfonyl cyclodextrin and allyloxybutyric acid into a flask, introduce nitrogen into the flask, stir to react, pour the solution into methanol to precipitate, filter, wash with ethanol, and dry to obtain allyloxybutyric acid cyclodextrin.

[0009] S2. Add water, allyloxybutyric acid cyclodextrin and benzophenone into a reaction dish, stir to dissolve, add spandex fabric, irradiate under ultraviolet light for 10-30 minutes, filter, wash and dry to obtain butyric acid cyclodextrin grafted spandex fabric.

[0010] S3. Add water and quaternized tannic acid into a flask, stir to dissolve, then add butyrate-based cyclodextrin grafted spandex fabric, heat to 40-50°C and stir for 4-10 hours, filter, wash with water, and dry to obtain modified spandex fabric.

[0011] Furthermore, the ratio of N,N-dimethylformamide, mono-6-oxy-toluenesulfonyl cyclodextrin, and allyloxybutyric acid in S1 is (10-20) mL: 1 g: (5-8) g.

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

[0013] Furthermore, the ratio of water, allyloxybutyric acid cyclodextrin and benzophenone in S2 is 1L:(10-50)g:(0.6-3)g.

[0014] Furthermore, the ratio of water to quaternized tannic acid in S3 is 1L:(2-10)g.

[0015] Furthermore, allyloxybutyric acid is prepared according to the following method: 1,4-dioxane, boc-4-amino-3-hydroxybutyric acid, allyl bromide and sodium hydride in a ratio of (15-25) mL: 1 g: (0.45-0.6) g: (0.2-0.3) g are added to a flask, the temperature is raised to 60-80 ° C and stirred for 3-6 hours, cooled, the solvent is removed by rotary evaporation, and the product is washed with ether; the product is added to an ethyl acetate solution of hydrogen chloride, stirred at room temperature for 2-3 hours, the solvent is removed by rotary evaporation, the product is washed with ether, and dried to obtain allyloxybutyric acid.

[0016] Furthermore, quaternary ammonium tannic acid is prepared according to the following method: acetone, tannic acid, 2,3-epoxypropyltrimethylammonium chloride, sodium hydroxide and water in a ratio of (8-15) mL1g: (0.3-0.8) g: (0.12-0.3) g: (8-15) mL are added to a flask, the temperature is raised to 50-70° C. and refluxed for 4-8 hours, cooled, 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.

[0017] The beneficial technical effect of the present invention is that in a sodium hydroxide system, the epoxy group of 2,3-epoxypropyltrimethylammonium chloride and the hydroxyl group of tannic acid are used to undergo a ring-opening reaction to obtain quaternized tannic acid. The quaternized tannic acid contains a bioactive polyphenol structure and an antibacterial quaternary ammonium salt structure, and has a highly effective antibacterial property.

[0018] In a sodium hydride catalytic system, boc-4-amino-3-hydroxybutyric acid reacts with allyl bromide, and Boc protection is removed with hydrochloric acid to obtain allyloxybutyric acid, which is then reacted with mono-6-oxy-p-toluenesulfonyl cyclodextrin to obtain allyloxybutyric acid cyclodextrin, thereby introducing alkenyl and carboxyl groups 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, which is convenient for subsequent grafting reactions.

[0019] Ultraviolet light irradiation grafting reaction is used to irradiate allyloxybutyric acid cyclodextrin on spandex fiber to obtain butyric acid cyclodextrin grafted spandex fabric, and finally quaternary ammonium tannic acid is included. The carboxyl group of cyclodextrin can electrostatically interact with quaternary ammonium tannic acid, thereby enhancing the inclusion effect of cyclodextrin on tannic acid and improving the inclusion rate, thereby increasing the loading capacity of spandex fabric on quaternary ammonium tannic acid, which is beneficial to enhancing the antibacterial properties of spandex fabric. In addition, no matter how many times the spandex fabric is washed, it still has long-lasting antibacterial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the reaction formula for the preparation of allyloxybutyric acid.

[0021] Figure 2 This is a reaction route for preparing allyloxybutyric acid-based cyclodextrin. DETAILED DESCRIPTION

[0022] In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0023] Mono-6-oxy-toluenesulfonyl cyclodextrin is prepared according to the following method: 10 g of β-cyclodextrin is added to a flask, 70 mL of water is added, the mixture is stirred thoroughly, 30 mL of 1 mol / L NaOH solution is added dropwise at 0°C, the mixture is stirred for 3 h, hydrochloric acid solution is added dropwise to the filtrate to adjust the pH to neutral after filtering, a precipitate is precipitated, the precipitate is added to waste water after filtering, the insoluble matter is removed by filtering while hot, the filtrate is allowed to stand at 0°C for 12 h, filtered, the solid product is collected, and recrystallized with water to obtain mono-6-oxy-toluenesulfonyl cyclodextrin.

[0024] Example 1

[0025] (1) Add 50 mL of acetone, 5 g of tannic acid, 1.5 g of 2,3-epoxypropyltrimethylammonium chloride, 0.6 g of sodium hydroxide and 50 mL of water into a flask, heat to 60° C. and reflux for 5 h, cool, dropwise add dilute hydrochloric acid for neutralization, remove the solvent by rotary evaporation, and recrystallize the product with ethanol to obtain quaternary ammonium tannic acid.

[0026] (2) Add 50 mL of 1,4-dioxane, 3 g of boc-4-amino-3-hydroxybutyric acid, 1.56 g of allyl bromide and 0.72 g of sodium hydride to a flask, heat to 70°C and stir for 6 h, cool, remove the solvent by rotary evaporation, and wash with ether; add the product to 50 mL of 4 mol / L hydrogen chloride in ethyl acetate solution, stir at room temperature for 2 h, remove the solvent by rotary evaporation, wash with ether, and dry to obtain allyloxybutyric acid.

[0027] (3) Add 5 mL of N,N-dimethylformamide, 0.5 g of mono-6-oxy-toluenesulfonyl cyclodextrin, and 3.2 g of allyloxybutyric acid into a flask, introduce nitrogen into the flask, raise the temperature to 80°C, react for 96 hours, pour the solution into methanol to precipitate, filter, wash with ethanol, and dry to obtain allyloxybutyric acid cyclodextrin.

[0028] (4) Add 50 mL of water, 0.5 g of allyloxybutyric acid cyclodextrin, and 0.03 g of benzophenone to a reaction dish, stir to dissolve, add spandex fabric, irradiate under an ultraviolet lamp with a power of 80 W for 20 min, filter, wash, and dry to obtain butyric acid cyclodextrin grafted spandex fabric.

[0029] (5) Add 1 L of water and 2 g of quaternized tannic acid into a flask and stir to dissolve. Then add butyrate-based cyclodextrin grafted spandex fabric, heat to 50 °C and stir for 8 h, filter, wash with water, and dry to obtain modified spandex fabric.

[0030] The difference between Example 2 and Example 1 is as follows: (1) 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 to a flask, the temperature was raised to 60° C. and refluxed for 5 h, the mixture was cooled, dilute hydrochloric acid was added dropwise for neutralization, the solvent was removed by rotary evaporation, and the product was recrystallized from ethanol to obtain quaternary ammonium tannic acid.

[0031] The difference between Example 3 and Example 1 is as follows: (1) 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 to a flask, the temperature was raised to 60° C. and refluxed for 5 h, the mixture was cooled, dilute hydrochloric acid was added dropwise for neutralization, the solvent was removed by rotary evaporation, and the product was recrystallized from ethanol to obtain quaternary ammonium tannic acid.

[0032] The difference between Example 4 and Example 2 is: (4) Add 50 mL of water, 1 g of allyloxybutyric acid cyclodextrin, and 0.06 g of benzophenone to a reaction dish, stir to dissolve, add spandex fabric, irradiate under an ultraviolet lamp with a power of 80 W for 20 min, filter, wash, and dry to obtain butyric acid cyclodextrin grafted spandex fabric.

[0033] The difference between Example 5 and Example 2 is: (4) Add 50 mL of water, 1.8 g of allyloxybutyric acid cyclodextrin, and 0.1 g of benzophenone to a reaction dish, stir to dissolve, add spandex fabric, irradiate under an ultraviolet lamp with a power of 80 W for 20 min, filter, wash, and dry to obtain butyric acid cyclodextrin grafted spandex fabric.

[0034] The difference between Example 6 and Example 2 is: (4) Add 50 mL of water, 2.5 g of allyloxybutyric acid cyclodextrin, and 0.15 g of benzophenone to a reaction dish, stir to dissolve, add spandex fabric, irradiate under an ultraviolet lamp with a power of 80 W for 20 min, filter, wash, and dry to obtain butyric acid cyclodextrin grafted spandex fabric.

[0035] The difference between Example 7 and Example 6 is: (5) Add 1L of water and 4g of quaternized tannic acid into a flask, stir to dissolve, then add butyrate-based cyclodextrin grafted spandex fabric, heat to 50°C and stir for 8h, filter, wash with water, and dry to obtain modified spandex fabric.

[0036] The difference between Example 8 and Example 6 is: (5) Add 1L of water and 6g of quaternized tannic acid into a flask, stir to dissolve, then add butyrate-based cyclodextrin grafted spandex fabric, heat to 50°C and stir for 8h, filter, wash with water, and dry to obtain modified spandex fabric.

[0037] The difference between Example 9 and Example 6 is: (5) Add 1L of water and 8g of quaternized tannic acid into a flask, stir to dissolve, then add butyrate-based cyclodextrin grafted spandex fabric, heat to 50°C and stir for 8h, filter, wash with water, and dry to obtain modified spandex fabric.

[0038] The difference between Example 10 and Example 6 is: (5) Add 1L of water and 10g of quaternized tannic acid into a flask, stir to dissolve, then add butyrate-based cyclodextrin grafted spandex fabric, heat to 50°C and stir for 8h, filter, wash with water, and dry to obtain modified spandex fabric.

[0039] The difference between Comparative Example 1 and Example 1 is as follows: (5) 1 L of water and 2 g of tannic acid were added to a flask, stirred to dissolve, and then butyrate-cyclodextrin-grafted spandex fabric was added, the temperature was raised to 50° C. and stirred for 8 h, filtered, washed with water, and dried to obtain modified spandex fabric.

[0040] The difference between Comparative Example 2 and Example 1 is: (5) Add 1L of water and 2g of 2,3-epoxypropyltrimethylammonium chloride to a flask, stir to dissolve, then add butyrate cyclodextrin grafted spandex fabric, heat to 50°C and stir for 8h, filter, wash with water, and dry to obtain modified spandex fabric.

[0041] Antibacterial test: Refer 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: Oscillation method" to test the antibacterial properties of modified spandex fabrics against Escherichia coli.

[0042] Washing resistance test: According to GB / T 8629-2001 "Household washing and drying procedures for textile testing", the modified spandex fabric prepared in Example 9 was subjected to a washing test, and the washing times were 10, 30, and 50 times, respectively. Then, an antibacterial test was performed.

[0043] Table 1 Antibacterial performance test 1

[0044] Antibacterial 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 butyrate-based cyclodextrin grafted spandex fabric prepared in step (4) of Example 1.

[0046] It can be seen from Examples 1-3 that the ratio of tannic acid (5 g) to 2,3-epoxypropyltrimethylammonium chloride (3 g) is 1:0.6, and the obtained quaternized tannic acid is incorporated into the modified spandex fabric, and the fabric has better antibacterial properties against Escherichia coli. With the increase in the amount of 2,3-epoxypropyltrimethylammonium chloride, the antibacterial rate of the fabric tends to decrease slightly.

[0047] In Comparative Example 1, the butyrate-cyclodextrin grafted spandex fabric includes tannic acid, and in Comparative Example 1, 2,3-epoxypropyltrimethylammonium chloride is included, and the antibacterial rates are both lower than those in Example 1.

[0048] Table 2 Antibacterial performance test 2

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

[0050] It can be seen from Examples 2 and 4-6 that during the UV grafting process, when the mass fraction of allyloxybutyric acid cyclodextrin in the solution was 36 g / L, the antibacterial rate of the modified spandex fabric against Escherichia coli reached 92.6%; when the mass fraction was 50 g / L, the antibacterial rate of the modified spandex fabric increased slightly to 93.3%.

[0051] Table 3 Antibacterial performance test three

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

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

[0054] Table 4 Antibacterial performance test 4

[0055]

[0056] After 50 washings, the antibacterial rate is still 92.0%.

[0057] The present invention may also have other various embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a modified spandex fabric, characterized in that: The modified spandex fabric is prepared according to the following method: S1. Add N,N-dimethylformamide, mono-6-oxy-toluenesulfonyl cyclodextrin and allyloxybutyric acid into a flask, introduce nitrogen into the flask, stir to react, pour the solution into methanol to precipitate, filter, wash and dry to obtain allyloxybutyric acid cyclodextrin; S2, add water, allyloxybutyric acid cyclodextrin, and benzophenone to a reaction dish, stir to dissolve, add spandex fabric, irradiate under ultraviolet light for 10-30 minutes, filter, wash, and dry to obtain butyric acid cyclodextrin grafted spandex fabric; S3. Add water and quaternized tannic acid into a flask, stir to dissolve, then add butyrate-based cyclodextrin grafted spandex fabric, heat to 40-50°C and stir for 4-10 hours, filter, wash with water, and dry to obtain modified spandex fabric.

2. The method for preparing the modified spandex fabric according to claim 1, characterized in that: The ratio of N,N-dimethylformamide, mono-6-oxy-toluenesulfonyl cyclodextrin and allyloxybutyric acid in S1 is (10-20) mL: 1 g: (5-8) g.

3. The method for preparing the modified spandex fabric according to claim 1, characterized in that: The reaction temperature in S1 is 75-90°C and the reaction time is 48-96h.

4. The method for preparing the modified spandex fabric according to claim 1, characterized in that: The ratio of water, allyloxybutyric acid cyclodextrin and benzophenone in S2 is 1L:(10-50)g:(0.6-3)g.

5. The method for preparing the modified spandex fabric according to claim 1, characterized in that: The ratio of water to quaternized tannic acid in S3 is 1L:(2-10)g.

6. The method for preparing the modified spandex fabric according to claim 2, characterized in that: The allyloxybutyric acid is prepared according to the following method: 1,4-dioxane, boc-4-amino-3-hydroxybutyric acid, allyl bromide and sodium hydride are added to a flask, the temperature is raised to 60-80° C. and stirred for 3-6 hours, cooled, the solvent is removed by rotary evaporation, and washed; the product is added to an ethyl acetate solution of hydrogen chloride, stirred at room temperature for 2-3 hours, the solvent is removed by rotary evaporation, washed, and dried to obtain the allyloxybutyric acid.

7. The method for preparing the modified spandex fabric according to claim 6, characterized in that: The ratio of 1,4-dioxane, boc-4-amino-3-hydroxybutyric acid, propylene bromide and sodium hydride is (15-25) mL: 1 g: (0.45-0.6) g: (0.2-0.3) g.

8. The method for preparing the modified spandex fabric according to claim 5, characterized in that: The quaternized tannic acid is prepared according to the following method: acetone, tannic acid, 2,3-epoxypropyltrimethylammonium chloride, sodium hydroxide and water are added into a flask, the temperature is raised to 50-70° C. and refluxed for 4-8 hours, the mixture is cooled, dilute hydrochloric acid is added dropwise for neutralization, rotary evaporation is performed, and recrystallization is performed to obtain the quaternized tannic acid.

9. The method for preparing the modified spandex fabric according to claim 8, characterized in that: The ratio of the acetone, tannic acid, 2,3-epoxypropyltrimethylammonium chloride, sodium hydroxide and water is (8-15) mL1g: (0.3-0.8) g: (0.12-0.3) g: (8-15) mL.

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