Preparation method of antibacterial elastic moisture absorption fiber

Abstract

The invention relates to the technical field of fibers, and discloses a preparation method of an antibacterial elastic moisture-absorbing fiber, which comprises the following steps: adding polyacrylonitrile, polyurethane resin and quaternary ammonium salt polyurethane-polyacrylonitrile into N, N-dimethylformamide, stirring, carrying out vacuum defoaming, and carrying out electrostatic spinning to obtain the antibacterial elastic moisture-absorbing fiber. The quaternary ammonium salt polyurethane-polyacrylonitrile simultaneously contains a polyacrylonitrile molecular main chain and a polyurethane molecular side chain, can be used as a compatilizer to improve the compatibility between polyacrylonitrile and polyurethane resin, is beneficial to improving the crimp elasticity recovery rate and moisture regain of polyacrylonitrile fibers, and shows better crimp elasticity and hydrophilic hygroscopicity. And the quaternary ammonium salt polyurethane-polyacrylonitrile contains a biquaternary ammonium salt antibacterial group, so that the antibacterial property of the polyacrylonitrile fiber is remarkably improved. The polyacrylonitrile fiber has better application in the aspect of high-elastic, hydrophilic, moisture-absorbing and antibacterial fabrics.

Description

Technical Field

[0001] The invention relates to the technical field of fibers, in particular to a method for preparing antibacterial elastic moisture-absorbing fibers. Background Art

[0002] Polyacrylonitrile fiber is widely used in clothing fabrics, carpets, fiber membranes, etc. However, traditional polyacrylonitrile fiber and its fabrics have low hydrophilicity and moisture absorption rate, poor wearing comfort, and poor elasticity and antibacterial properties. Improving the hydrophilicity, moisture absorption, elasticity and antibacterial properties of polyacrylonitrile fiber can make polyacrylonitrile fiber have better application in high-end clothing fabrics and textiles.

[0003] Adding organic antibacterial agents such as quaternary ammonium salts and inorganic antibacterial agents such as nanosilver to polyacrylonitrile fibers can improve the antibacterial properties of the fibers. Polyurethane fibers have very high resilience and tensile strength. The patent with publication number CN117286637A discloses a unidirectional moisture-conducting antibacterial polyurethane / polyacrylonitrile Janus nanofiber membrane and its preparation method. A bulk antibacterial polyurethane PQU is prepared using QAS as a chain extender, and then an antibacterial PU / PAN Janus membrane with unidirectional moisture-conducting properties is prepared by layer-by-layer electrostatic spinning technology, which has good antibacterial properties and unidirectional water transmission properties. However, the patent does not improve the curling elasticity, moisture regain and other properties of polyacrylonitrile fibers. Summary of the invention

[0004] The invention solves the problem of poor mechanical properties of polyacrylonitrile and improves the antibacterial property of polyacrylonitrile fiber.

[0005] Technical solution: A method for preparing antibacterial elastic moisture-absorbing fiber:

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

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

[0008] .

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

[0010] .

[0011] S3: Add polyacrylonitrile, polyurethane resin, and quaternary ammonium polyurethane-polyacrylonitrile to N,N-dimethylformamide, stir and then perform vacuum degassing, and perform electrospinning with a spinning solution flow rate of 0.3-0.6 mL / h and a spinning voltage of 18-20 kV to obtain an antibacterial elastic hygroscopic fiber.

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

[0013] Preferably, the mass ratio of hydroxyethyl polyacrylonitrile, dihydroxyimidazole quaternary ammonium salt, diisocyanate compound and dibutyltin dilaurate in S2 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, the mass ratio of polyacrylonitrile, polyurethane resin, and quaternary ammonium salt polyurethane-polyacrylonitrile in S3 is (75-90): (10-25): (1-6).

[0016] (III) Beneficial effects of the present invention: The present invention electrostatically spins polyacrylonitrile, polyurethane resin, and quaternary ammonium salt polyurethane-polyacrylonitrile. Quaternary ammonium salt polyurethane-polyacrylonitrile contains both the main chain of polyacrylonitrile molecules and the side chain of polyurethane molecules, which 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 spinning, which is beneficial to improving the curl elastic recovery rate and moisture regain of polyacrylonitrile fiber, showing better curl elasticity and hydrophilic hygroscopicity. In addition, quaternary ammonium salt polyurethane-polyacrylonitrile contains a diquaternary ammonium salt antibacterial group, which significantly improves the antibacterial properties of polyacrylonitrile fiber. This enables polyacrylonitrile fiber to have better applications in high elasticity, hydrophilic hygroscopicity and antibacterial fabrics. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention is described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. 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.

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

[0019] Embodiment 1:

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

[0021] (2): Add 9.7 g acrylonitrile and 0.3 g hydroxyethyl methacrylate to 40 mL water, stir and heat to 70 °C in a nitrogen atmosphere, add 18 mg ammonium persulfate and 6 mg 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 heat to 75 °C in a nitrogen atmosphere, 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 and filter, wash with ethanol and dry to obtain quaternary ammonium polyurethane-polyacrylonitrile.

[0023] (4): Add 900 g of polyacrylonitrile, 100 g of polyurethane resin, and 10 g of quaternary ammonium polyurethane-polyacrylonitrile to 6 L of N,N-dimethylformamide, stir and vacuum degass, and perform electrospinning with a spinning solution flow rate of 0.4 mL / h and a spinning voltage of 20 kV to obtain an antibacterial elastic hygroscopic fiber.

[0024] Embodiment 2:

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

[0026] (2): Add 9.8 g acrylonitrile and 0.2 g hydroxyethyl methacrylate to 40 mL water, stir and heat to 60 °C in a nitrogen atmosphere, add 18 mg ammonium persulfate and 7 mg sodium bisulfite, stir and react for 4 h, filter, 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, stir and heat to 65 °C in a nitrogen atmosphere, add 2.4 g of dihydroxyimidazole quaternary ammonium 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 polyurethane-polyacrylonitrile.

[0028] (4): Add 850g polyacrylonitrile, 150g polyurethane resin and 35g quaternary ammonium polyurethane-polyacrylonitrile to 6L N,N-dimethylformamide, stir and vacuum degass, and perform electrospinning with a spinning solution flow rate of 0.3mL / h and a spinning voltage of 20kV to obtain antibacterial elastic hygroscopic fiber.

[0029] Embodiment 3:

[0030] (1): Add 30 mmol 1-(2-hydroxyethyl)imidazole and 15 mmol 1,4-dichlorobenzyl to 50 mL acetonitrile, heat to 85°C, condense and reflux for 36 hours, rotary evaporate, wash with petroleum ether, and recrystallize the product in acetonitrile to obtain dihydroxyimidazole quaternary ammonium salt.

[0031] (2): Add 9.5 g acrylonitrile and 0.5 g hydroxyethyl methacrylate to 30 mL water, stir and heat to 55 °C in a nitrogen atmosphere, add 14 mg ammonium persulfate and 5 mg sodium bisulfite, stir and react for 4 h, filter, 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, stir and heat to 80 °C in a nitrogen atmosphere, add 3.3 g of dihydroxyimidazole quaternary ammonium 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 polyurethane-polyacrylonitrile.

[0033] (4): Add 800 g of polyacrylonitrile, 200 g of polyurethane resin, and 60 g of quaternary ammonium polyurethane-polyacrylonitrile to 6 L of N,N-dimethylformamide, stir and vacuum degass, and perform electrospinning with a spinning solution flow rate of 0.6 mL / h and a spinning voltage of 18 kV to obtain antibacterial elastic hygroscopic fibers.

[0034] Embodiment 4:

[0035] (1): Add 20 g of hydroxyethyl polyacrylonitrile (prepared in the same manner as in Example 1) to 300 mL of N,N-dimethylformamide, stir and heat to 80°C in a nitrogen atmosphere, add 2.9 g of dihydroxyimidazole quaternary ammonium 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 and filter, wash with ethanol and dry to obtain quaternary ammonium polyurethane-polyacrylonitrile.

[0036] (2): Add 750g polyacrylonitrile, 250g polyurethane resin and 60g quaternary ammonium polyurethane-polyacrylonitrile to 6L N,N-dimethylformamide, stir and vacuum degass, and perform electrospinning with a spinning solution flow rate of 0.6mL / h and a spinning voltage of 18kV to obtain antibacterial elastic hygroscopic fiber.

[0037] Comparative Example 1:

[0038] (1): Add 900 g of polyacrylonitrile to 6 L of N,N-dimethylformamide, stir and vacuum degass, and perform electrospinning at a spinning solution flow rate of 0.4 mL / h and a spinning voltage of 20 kV to obtain polyacrylonitrile fiber.

[0039] Comparative Example 2:

[0040] (1): Add 900 g of polyacrylonitrile and 100 g of polyurethane resin to 6 L of N,N-dimethylformamide, stir and vacuum degass, and perform electrospinning at a spinning solution flow rate of 0.4 mL / h and a spinning voltage of 20 kV to obtain polyacrylonitrile fiber.

[0041] Comparative Example 3:

[0042] (1): Add 900 g of polyacrylonitrile and 10 g of quaternary ammonium polyurethane-polyacrylonitrile (prepared in the same manner as in Example 1) to 6 L of N,N-dimethylformamide, stir and vacuum degas, and perform electrospinning at a spinning solution flow rate of 0.4 mL / h and a spinning voltage of 20 kV to obtain polyacrylonitrile fiber.

[0043] Comparative Example 4:

[0044] (1): Add 20 g of hydroxyethyl polyacrylonitrile (prepared in the same manner as in Example 1) to 400 mL of N,N-dimethylformamide, stir and 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 and 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, stir and vacuum degass, and perform electrospinning with a spinning solution flow rate of 0.4 mL / h and a spinning voltage of 20 kV to obtain polyacrylonitrile fiber.

[0046] Comparative Example 5:

[0047] (1): Under nitrogen atmosphere, 3.6 g of dihydroxyimidazole quaternary ammonium salt (prepared in the same manner as in Example 1), 4.4 g of isophorone diisocyanate, and 18 mg of dibutyltin dilaurate were added to 400 mL of N,N-dimethylformamide at 75°C, and the mixture was stirred for 3 h. Ethanol was added to the solution, and the mixture was filtered after stirring. The solution was washed with ethanol and dried to obtain a quaternary ammonium polyurethane.

[0048] (2): Add 900 g of polyacrylonitrile, 100 g of polyurethane resin, and 10 g of quaternary ammonium polyurethane to 6 L of N,N-dimethylformamide, stir and vacuum degass, and perform electrospinning with a spinning solution flow rate of 0.4 mL / h and a spinning voltage of 20 kV to obtain polyacrylonitrile fiber.

[0049] The fiber curl elasticity was tested according to GB / T 14338-2008.

[0050] The moisture regain of the fiber was tested according to GB / T 9995-1997 standard.

[0051] The antibacterial rate and antibacterial properties of the fiber were tested according to GB / T 20944.3-2008 standard.

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

[0053] Table 1

[0054]

[0055] After testing, as shown in Table 1, compared with the comparative examples, the polyacrylonitrile fibers of the embodiments added with polyurethane resin and quaternary ammonium polyurethane-polyacrylonitrile have higher curl elastic recovery rate, moisture regain and antibacterial rate, showing good curl elasticity, hydrophilic hygroscopicity and antibacterial properties.

Claims

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

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

3. The method for preparing the antibacterial elastic moisture-absorbing fiber according to claim 1, characterized in that: The reaction temperature in S1 is 55-70°C and the reaction time is 2-4h.

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

5. The method for preparing the antibacterial elastic moisture-absorbing fiber according to claim 4, characterized in that: The diisocyanate compound is isophorone diisocyanate, toluene diisocyanate or hexamethylene diisocyanate.

6. The method for preparing the antibacterial elastic moisture-absorbing fiber according to claim 4, characterized in that: The preparation method of the dihydroxy imidazole quaternary ammonium salt comprises: adding 1-(2-hydroxyethyl) imidazole and 1,4-dichlorobenzyl in a molar ratio of (2-2.2):1 to acetonitrile, heating to 80-85° C., condensing and refluxing for 36-48 hours, rotary evaporation, washing with petroleum ether, and recrystallizing the product in acetonitrile to obtain the dihydroxy imidazole quaternary ammonium salt.

7. The method for preparing the antibacterial elastic moisture-absorbing fiber according to claim 1, characterized in that: The reaction temperature in S2 is 65-80°C and the reaction time is 2-3h.

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

9. The method for preparing the antibacterial elastic moisture-absorbing fiber according to claim 1, characterized in that: During electrospinning in S3, the spinning solution flow rate is 0.3-0.6 mL / h, and the spinning voltage is 18-20 kV.

Images