Preparation method of an antibacterial elastic moisture-absorbing fiber

Abstract

The present invention relates to the field of fiber technology, and discloses a preparation method of an antibacterial elastic moisture-absorbing fiber. Polyacrylonitrile, polyurethane resin, and quaternary ammonium salt polyurethane-polyacrylonitrile are added to N,N-dimethylformamide, stirred and then degassed under vacuum, and electrospun to obtain the antibacterial elastic moisture-absorbing fiber. Quaternary ammonium salt polyurethane-polyacrylonitrile contains both a polyacrylonitrile molecular main chain and a polyurethane molecular side chain, and can be used as a compatibilizer to improve the compatibility between polyacrylonitrile and polyurethane resin, which is beneficial to improving the crimp elastic recovery rate and moisture regain of polyacrylonitrile fibers, showing better crimp elasticity, hydrophilic moisture absorption. And quaternary ammonium salt polyurethane-polyacrylonitrile contains a bisquaternary ammonium salt antibacterial group, which significantly improves the antibacterial performance of polyacrylonitrile fibers. It enables polyacrylonitrile fibers to have better applications in high-elastic, hydrophilic moisture-absorbing and antibacterial fabrics.

Description

Technical Field

[0001] The present invention relates to the technical field of fibers, and specifically to a preparation method of antibacterial elastic moisture-absorbing fibers. Background Art

[0002] Polyacrylonitrile fibers are widely used in clothing fabrics, carpets, fiber membranes, etc. However, traditional polyacrylonitrile fibers and their fabric materials have low hydrophilicity and moisture absorption rate, poor wearing comfort, and poor performance in improving elasticity and antibacterial properties. Improving the hydrophilic moisture absorption, elasticity, and antibacterial properties of polyacrylonitrile fibers can enable polyacrylonitrile fibers to have better applications in high-grade clothing fabrics and textiles.

[0003] Adding organic antibacterial agents such as quaternary ammonium salts and inorganic antibacterial agents such as nano silver to polyacrylonitrile fibers can improve the antibacterial properties of the fibers. Polyurethane fibers have high resilience, tensile resistance, and other properties. The patent with the publication number CN117286637A discloses a unidirectional moisture-permeable antibacterial polyurethane / polyacrylonitrile Janus nanofiber membrane and its preparation method. A bulk antibacterial polyurethane PQU was prepared using QAS as a chain extender, and then an antibacterial PU / PAN Janus membrane with unidirectional moisture transfer characteristics was prepared by layer-by-layer electrospinning technology, which has good antibacterial properties and unidirectional water transfer characteristics. However, this patent does not improve the crimp elasticity, moisture regain rate, and other properties of polyacrylonitrile fibers. Summary of the Invention

[0004] The present invention solves the problem of poor mechanical properties of polyacrylonitrile and at the same time improves the antibacterial property of polyacrylonitrile fibers.

[0005] Technical Solution: A preparation method of antibacterial elastic moisture-absorbing fibers:

[0006] S1: Add acrylonitrile and 2-hydroxyethyl methacrylate to water, stir, and then heat to 55 - 70°C in a nitrogen atmosphere. Add ammonium persulfate and sodium bisulfite, stir and react for 2 - 4 h. After filtration, wash with water and ethanol, and dry to obtain hydroxyethyl polyacrylonitrile.

[0007] S2: Add hydroxyethyl polyacrylonitrile to N,N-dimethylformamide, stir, and then heat to 65 - 80°C in a nitrogen atmosphere. Add dihydroxyimidazolium quaternary salt, diisocyanate compound, and dibutyltin dilaurate, stir and react for 2 - 3 h. Add ethanol to the solution, stir, filter, wash with ethanol, and dry to obtain quaternary ammonium salt polyurethane-polyacrylonitrile. The reaction formula is:

[0008] .

[0009] Preferably, the preparation method of the dihydroxyimidazole quaternary ammonium salt is as follows: Add 1-(2-hydroxyethyl)imidazole and 1,4-dichlorobenzyl with a molar ratio of (2-2.2):1 to acetonitrile, heat to 80-85 °C, carry out condensation reflux reaction for 36-48 h, perform rotary evaporation, wash with petroleum ether, and recrystallize the product in acetonitrile to obtain the dihydroxyimidazole quaternary ammonium salt. The reaction formula is as follows:

[0010] .

[0011] S3: Add polyacrylonitrile, polyurethane resin, and quaternary ammonium salt polyurethane-polyacrylonitrile to N,N-dimethylformamide, stir and then degas under vacuum, carry out electrospinning, the flow rate of the spinning solution is 0.3-0.6 mL / h, and the spinning voltage is 18-20 kV to obtain antibacterial elastic hygroscopic fibers.

[0012] Preferably, in S1, the molar ratio of acrylonitrile, 2-hydroxyethyl methacrylate, ammonium persulfate, and sodium bisulfite is (95-98):(2-5):(0.14-0.18):(0.05-0.07).

[0013] Preferably, in S2, the mass ratio of hydroxyethyl polyacrylonitrile, dihydroxyimidazole quaternary ammonium salt, diisocyanate compound, and dibutyltin dilaurate is 100:(12-18):(16-22):(0.07-0.1).

[0014] Preferably, the diisocyanate compound is isophorone diisocyanate, toluene diisocyanate, or hexamethylene diisocyanate.

[0015] Preferably, in S3, the mass ratio of polyacrylonitrile, polyurethane resin, and quaternary ammonium salt polyurethane-polyacrylonitrile is (75-90):(10-25):(1-6).

[0016] (III) Beneficial effects of the present invention: In the present invention, polyacrylonitrile, polyurethane resin, and quaternary ammonium salt polyurethane-polyacrylonitrile are blended and electrospun. The quaternary ammonium salt polyurethane-polyacrylonitrile contains both the polyacrylonitrile molecular main chain and the polyurethane molecular side chain, and can be used as a compatibilizer to improve the compatibility between polyacrylonitrile and polyurethane resin. The polyurethane resin itself has excellent elasticity, toughness, and hydrophilicity, and forms a highly compatible composite fiber with polyacrylonitrile by spinning, which is beneficial to improving the crimp elastic recovery rate and moisture regain of polyacrylonitrile fibers, and shows better crimp elasticity, hydrophilic hygroscopicity. And the quaternary ammonium salt polyurethane-polyacrylonitrile contains a bisquaternary ammonium salt antibacterial group, which significantly improves the antibacterial performance of polyacrylonitrile fibers. It enables polyacrylonitrile fibers to have better applications in high-elastic, hydrophilic hygroscopic, and antibacterial fabrics. Specific embodiments

[0017] To make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions in the present invention will be described clearly and completely below. Apparently, the described embodiments are some but not all of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without any creative effort fall within the scope of protection of the present invention.

[0018] Polyacrylonitrile, Dongguan Shengbang High Polymer Materials Co., Ltd. Polyurethane resin, Dongguan Hongke Plastic Raw Materials Co., Ltd.

[0019] Example 1:

[0020] (1): Add 30 mmol of 1-(2-hydroxyethyl)imidazole and 15 mmol of 1,4-p-dichlorobenzyl to 50 mL of acetonitrile, heat to 80 °C, carry out condensation reflux reaction for 48 h, rotary evaporate, wash with petroleum ether, and recrystallize the product in acetonitrile to obtain dihydroxyimidazole quaternary ammonium salt.

[0021] (2): Add 9.7 g of acrylonitrile and 0.3 g of 2-hydroxyethyl methacrylate to 40 mL of water, stir, and under a nitrogen atmosphere, heat to 70 °C, add 18 mg of ammonium persulfate and 6 mg of sodium bisulfite, stir and react for 2 h, filter, wash with water and ethanol, and dry to obtain hydroxyethyl polyacrylonitrile.

[0022] (3): Add 20 g of hydroxyethyl polyacrylonitrile to 400 mL of N,N-dimethylformamide, stir, and under a nitrogen atmosphere, heat to 75 °C, add 3.6 g of dihydroxyimidazole quaternary ammonium salt, 4.4 g of isophorone diisocyanate, and 18 mg of dibutyltin dilaurate, stir and react for 3 h, add ethanol to the solution, stir, filter, wash with ethanol, and dry to obtain quaternary ammonium salt polyurethane-polyacrylonitrile.

[0023] (4): Add 900 g of polyacrylonitrile, 100 g of polyurethane resin, and 10 g of quaternary ammonium salt polyurethane-polyacrylonitrile to 6 L of N,N-dimethylformamide, stir, carry out vacuum degassing, and perform electrospinning. The flow rate of the spinning solution is 0.4 mL / h, and the spinning voltage is 20 kV to obtain antibacterial elastic hygroscopic fibers.

[0024] Example 2:

[0025] (1): Add 33 mmol of 1-(2-hydroxyethyl)imidazole and 15 mmol of 1,4-p-dichlorobenzyl to 60 mL of acetonitrile, heat to 80 °C, carry out condensation reflux reaction for 36 h, rotary evaporate, wash with petroleum ether, and recrystallize the product in acetonitrile to obtain dihydroxyimidazole quaternary ammonium salt.

[0026] (2): Add 9.8 g of acrylonitrile and 0.2 g of 2-hydroxyethyl methacrylate to 40 mL of water. After stirring, heat to 60 °C in a nitrogen atmosphere, add 18 mg of ammonium persulfate and 7 mg of sodium bisulfite, stir and react for 4 h. After filtration, wash with water and ethanol, and dry to obtain hydroxyethyl polyacrylonitrile.

[0027] (3): Add 20 g of hydroxyethyl polyacrylonitrile to 400 mL of N,N-dimethylformamide. After stirring, heat to 65 °C in a nitrogen atmosphere, add 2.4 g of dihydroxyimidazolium quaternary salt, 3.2 g of hexamethylene diisocyanate, and 20 mg of dibutyltin dilaurate, stir and react for 3 h. Add ethanol to the solution, stir and filter, wash with ethanol, and dry to obtain quaternary ammonium salt polyurethane-polyacrylonitrile.

[0028] (4): Add 850 g of polyacrylonitrile, 150 g of polyurethane resin, and 35 g of quaternary ammonium salt polyurethane-polyacrylonitrile to 6 L of N,N-dimethylformamide. After stirring, degas under vacuum, and perform electrospinning. The flow rate of the spinning solution is 0.3 mL / h, and the spinning voltage is 20 kV to obtain antibacterial elastic hygroscopic fibers.

[0029] Example 3:

[0030] (1): Add 30 mmol of 1-(2-hydroxyethyl)imidazole and 15 mmol of 1,4-dichlorobenzyl to 50 mL of acetonitrile. Heat to 85 °C, carry out reflux condensation reaction for 36 h, rotary evaporate, wash with petroleum ether, and recrystallize the product in acetonitrile to obtain dihydroxyimidazolium quaternary salt.

[0031] (2): Add 9.5 g of acrylonitrile and 0.5 g of 2-hydroxyethyl methacrylate to 30 mL of water. After stirring, heat to 55 °C in a nitrogen atmosphere, add 14 mg of ammonium persulfate and 5 mg of sodium bisulfite, stir and react for 4 h. After filtration, wash with water and ethanol, and dry to obtain hydroxyethyl polyacrylonitrile.

[0032] (3): Add 20 g of hydroxyethyl polyacrylonitrile to 300 mL of N,N-dimethylformamide. After stirring, heat to 80 °C in a nitrogen atmosphere, add 3.3 g of dihydroxyimidazolium quaternary salt, 4.1 g of toluene diisocyanate, and 14 mg of dibutyltin dilaurate, stir and react for 3 h. Add ethanol to the solution, stir and filter, wash with ethanol, and dry to obtain quaternary ammonium salt polyurethane-polyacrylonitrile.

[0033] (4): Add 800 g of polyacrylonitrile, 200 g of polyurethane resin, and 60 g of quaternary ammonium salt polyurethane-polyacrylonitrile to 6 L of N,N-dimethylformamide. After stirring, degas under vacuum, and perform electrospinning. The flow rate of the spinning solution is 0.6 mL / h, and the spinning voltage is 18 kV to obtain antibacterial elastic hygroscopic fibers.

[0034] Example 4:

[0035] (1): Add 20 g of hydroxyethyl polyacrylonitrile (prepared in the same way as in Example 1) to 300 mL of N,N-dimethylformamide. After stirring, heat to 80 °C in a nitrogen atmosphere, add 2.9 g of dihydroxyimidazolium quaternary salt, 3.7 g of toluene diisocyanate, and 14 mg of dibutyltin dilaurate. Stir and react for 2 h. Add ethanol to the solution, stir, filter, wash with ethanol, and dry to obtain quaternary ammonium salt polyurethane-polyacrylonitrile.

[0036] (2): Add 750 g of polyacrylonitrile, 250 g of polyurethane resin, and 60 g of quaternary ammonium salt polyurethane-polyacrylonitrile to 6 L of N,N-dimethylformamide. After stirring, degas under vacuum and perform electrospinning. The flow rate of the spinning solution is 0.6 mL / h, and the spinning voltage is 18 kV to obtain antibacterial elastic hygroscopic fibers.

[0037] Comparative Example 1:

[0038] (1): Add 900 g of polyacrylonitrile to 6 L of N,N-dimethylformamide. After stirring, degas under vacuum and perform electrospinning. The flow rate of the spinning solution is 0.4 mL / h, and the spinning voltage is 20 kV to obtain polyacrylonitrile fibers.

[0039] Comparative Example 2:

[0040] (1): Add 900 g of polyacrylonitrile and 100 g of polyurethane resin to 6 L of N,N-dimethylformamide. After stirring, degas under vacuum and perform electrospinning. The flow rate of the spinning solution is 0.4 mL / h, and the spinning voltage is 20 kV to obtain polyacrylonitrile fibers.

[0041] Comparative Example 3:

[0042] (1): Add 900 g of polyacrylonitrile and 10 g of quaternary ammonium salt polyurethane-polyacrylonitrile (prepared in the same way as in Example 1) to 6 L of N,N-dimethylformamide. After stirring, degas under vacuum and perform electrospinning. The flow rate of the spinning solution is 0.4 mL / h, and the spinning voltage is 20 kV to obtain polyacrylonitrile fibers.

[0043] Comparative Example 4:

[0044] (1): Add 20 g of hydroxyethyl polyacrylonitrile (prepared in the same way as in Example 1) to 400 mL of N,N-dimethylformamide. After stirring, heat to 75 °C in a nitrogen atmosphere, add 4.4 g of isophorone diisocyanate and 18 mg of dibutyltin dilaurate. Stir and react for 3 h. Add ethanol to the solution, stir, filter, wash with ethanol, and dry to obtain polyurethane-polyacrylonitrile.

[0045] (2): Add 900 g of polyacrylonitrile, 100 g of polyurethane resin, and 10 g of polyurethane-polyacrylonitrile to 6 L of N,N-dimethylformamide. After stirring, degas under vacuum and perform electrospinning. The flow rate of the spinning solution is 0.4 mL / h, and the spinning voltage is 20 kV to obtain polyacrylonitrile fibers.

[0046] Comparative Example 5:

[0047] (1): Under a nitrogen atmosphere, add 3.6 g of dihydroxyimidazolium quaternary salt (prepared in the same way as in Example 1), 4.4 g of isophorone diisocyanate, and 18 mg of dibutyltin dilaurate to 400 mL of N,N-dimethylformamide at 75 °C. Stir and react for 3 h. Add ethanol to the solution, stir, filter, wash with ethanol, and dry to obtain quaternary ammonium salt polyurethane.

[0048] (2): Add 900 g of polyacrylonitrile, 100 g of polyurethane resin, and 10 g of quaternary ammonium salt polyurethane to 6 L of N,N-dimethylformamide. After stirring, degas under vacuum and perform electrospinning. The flow rate of the spinning solution is 0.4 mL / h, and the spinning voltage is 20 kV to obtain polyacrylonitrile fibers.

[0049] Test the crimp elasticity of the fibers according to the GB / T 14338-2008 standard.

[0050] Test the moisture regain of the fibers according to the GB / T 9995-1997 standard.

[0051] Test the antibacterial rate and antibacterial properties of the fibers according to the GB / T 20944.3-2008 standard.

[0052] Antibacterial rate Y = (W - Q) / W × 100%. W is the average viable bacteria concentration (CFU / mL) in the flask after 18 h of oscillating contact with 3 control samples (the polyacrylonitrile fibers of Comparative Example 1). Q is the average viable bacteria concentration (CFU / mL) in the flask after 18 h of oscillating contact with 3 experimental samples (Examples 1-3 and Comparative Examples 2-4 respectively).

[0053] Table 1

[0054]

[0055] After testing, as shown in Table 1, compared with each comparative example, the polyacrylonitrile fibers of each example added polyurethane resin and quaternary ammonium salt polyurethane-polyacrylonitrile, and they have higher crimp elasticity recovery rate, moisture regain, and antibacterial rate, showing good crimp elasticity, hydrophilic moisture absorption, and antibacterial properties.

Claims

1. A method for preparing an antibacterial elastic hygroscopic fiber, characterized in that, The preparation method is as follows: S1: Add acrylonitrile and 2-hydroxyethyl methacrylate to water. After stirring, heat to the reaction temperature in a nitrogen atmosphere, add ammonium persulfate and sodium bisulfite, stir and react, filter, wash with water and ethanol, and dry to obtain hydroxyethyl polyacrylonitrile; S2: Add hydroxyethyl polyacrylonitrile to N,N-dimethylformamide. After stirring, heat to the reaction temperature in a nitrogen atmosphere, and add a dihydroxyimidazole quaternary ammonium salt, a diisocyanate compound, and dibutyltin dilaurate. Stir and react. Add ethanol to the solution, stir, filter, wash with ethanol, and dry to obtain a quaternary ammonium salt polyurethane-polyacrylonitrile; The dihydroxyimidazole quaternary ammonium salt, the diisocyanate compound, and the dibutyltin dilaurate are added, stirred and reacted, ethanol is added to the solution, stirred, filtered, washed with ethanol, and dried to obtain a quaternary ammonium salt polyurethane-polyacrylonitrile; S3: Add polyacrylonitrile, polyurethane resin, and quaternary ammonium salt polyurethane-polyacrylonitrile to N,N-dimethylformamide. After stirring, degas under vacuum and perform electrospinning to obtain antibacterial elastic hygroscopic fibers.

2. The preparation method of the antibacterial elastic hygroscopic fiber according to claim 1, characterized in that, In S1, the molar ratio of acrylonitrile, 2-hydroxyethyl methacrylate, ammonium persulfate, and sodium bisulfite is (95-98):(2-5):(0.14-0.18):(0.05-0.07).

3. The preparation method of the antibacterial elastic hygroscopic fiber according to claim 1, characterized in that, In S1, the reaction temperature is 55-70 °C and the reaction time is 2-4 h.

4. The preparation method of the antibacterial elastic hygroscopic fiber according to claim 1, characterized in that, In S2, the mass ratio of hydroxyethyl polyacrylonitrile, dihydroxyimidazolium quaternary salt, diisocyanate compound, and dibutyltin dilaurate is 100:(12-18):(16-22):(0.07-0.1).

5. The preparation method of the antibacterial elastic hygroscopic fiber according to claim 4, characterized in that, The diisocyanate compound is isophorone diisocyanate, toluene diisocyanate, or hexamethylene diisocyanate.

6. The preparation method of the antibacterial elastic hygroscopic fiber according to claim 4, characterized in that, The preparation method of the dihydroxyimidazolium quaternary salt is as follows: Add 1-(2-hydroxyethyl)imidazole and 1,4-dichlorobenzyl with a molar ratio of (2-2.2):1 to acetonitrile, heat to 80-85 °C, condense and reflux for 36-48 h, perform rotary evaporation, wash with petroleum ether, and recrystallize the product in acetonitrile to obtain the dihydroxyimidazolium quaternary salt.

7. The preparation method of the antibacterial elastic hygroscopic fiber according to claim 1, characterized in that, In S2, the reaction temperature is 65-80 °C and the reaction time is 2-3 h.

8. The preparation method of the antibacterial elastic hygroscopic fiber according to claim 1, characterized in that, In S3, the mass ratio of polyacrylonitrile, polyurethane resin, and quaternary ammonium salt polyurethane-polyacrylonitrile is (75-90):(10-25):(1-6).

9. The preparation method of the antibacterial elastic hygroscopic fiber according to claim 1, characterized in that, In S3, during electrospinning, the flow rate of the spinning solution is 0.3-0.6 mL / h and the spinning voltage is 18-20 kV.

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