Graphene chinlon spinning fiber and its preparation process

Abstract

The application relates to the technical field of spinning fibers, and discloses a graphene chinlon spinning fiber and a preparation process thereof; modified graphene A and modified graphene B are prepared; the raw materials of the modified graphene A include carboxyl activated graphene and tetramer lysine; the modified graphene A is used for preparing an impregnation solution together with glutaraldehyde, ethanol, propanol and sodium carbonate, and is used for surface modification of modified chinlon fibers prepared in a subsequent step; the raw materials of the modified graphene B include carboxyl activated graphene and a polyamide polyether block copolymer; the modified graphene B is used for preparing modified nylon 6 together with caprolactam and 6-aminohexanoic acid, and then the modified nylon 6 is subjected to melt spinning and post-drawing to obtain modified chinlon fibers; the modified chinlon fibers are put into the impregnation solution, impregnated at 50-60 DEG C for 0.5-1 h, the bath ratio is 1:50-1:60, and the graphene chinlon spinning fiber is obtained by taking out and drying; the graphene chinlon spinning fiber has good antibacterial property, hydrophilicity, good strength and excellent performance.

Description

Technical Field

[0001] This invention relates to the field of spinning fiber technology, and discloses a graphene nylon spinning fiber and its preparation process. Background Technology

[0002] Polyamide is a polymer formed by the polymerization of monomers containing carboxyl and amino groups through amide bonds. When used as synthetic fibers, it is called nylon. Among them, PA-6 and PA-66 are mainly used to spin synthetic fibers, called nylon 6 and nylon 66, which have good comprehensive properties.

[0003] With the increasing demand for products in diversified markets, single nylon fibers can no longer meet practical needs. Therefore, graphene modification is often added. Graphene has excellent hydrophilicity, infrared heating properties, antibacterial properties, and UV protection properties, while also improving the strength of nylon fibers, showing broad application prospects. However, the lack of functional groups on the surface of graphene leads to poor dispersibility, which severely limits its application in modified nylon materials.

[0004] Therefore, it is of great significance to prepare a graphene-nylon spinning fiber with good antibacterial properties, hydrophilicity, high strength, and excellent performance. Summary of the Invention

[0005] The purpose of this invention is to provide a graphene nylon spun fiber and its preparation process to solve the problems mentioned in the background art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] A process for preparing graphene nylon spun fiber includes the following steps: S1: Take carboxyl-activated graphene and polylysine to obtain modified graphene A;

[0008] S2: Take carboxyl-activated graphene, polyamide-polyether block copolymer, and water to prepare modified graphene B; take caprolactam, 6-aminohexanoic acid, and modified graphene B to prepare modified nylon 6; and melt spin and then stretch the modified nylon 6 to obtain modified nylon fiber.

[0009] S3: Take modified graphene A, glutaraldehyde, ethanol, propanol and sodium carbonate, stir evenly to obtain impregnation solution, put the modified nylon fiber into the impregnation solution, impregnate, take it out and dry to obtain graphene nylon spun fiber.

[0010] More preferably, the impregnation solution comprises the following raw materials: 5-15 parts modified graphene A, 1-2 parts glutaraldehyde, 600-700 parts ethanol, 50-100 parts propanol, and 1-2 parts sodium carbonate.

[0011] In a more optimized manner, the preparation of the modified graphene A includes the following steps: taking carboxylated graphene and water, ultrasonically dispersing for 1-2 hours to obtain a dispersion, adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, stirring for 1-2 hours to obtain carboxylated activated graphene; adding tetralysine, heating to 120-140°C and stirring for 10-14 hours, washing and drying to obtain modified graphene A.

[0012] In a more optimized manner, the modified graphene A comprises the following raw materials, by mass parts: 3-6 parts of carboxylated graphene, 1-2 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 2-4 parts of tetralysine; the concentration of the dispersion is 1 mg / mL.

[0013] In a more optimized manner, the preparation of the modified nylon 6 includes the following steps: taking carboxyl-activated graphene, polyamide-polyether block copolymer, and water, stirring evenly, heating to 120-140℃ and stirring for 10-14 hours, drying to obtain modified graphene B; taking caprolactam, 6-aminohexanoic acid, and modified graphene B, turning on the reflux condenser, introducing nitrogen gas, heating to 250-260℃ to melt the above substances, stirring for 6-7 hours to obtain modified nylon 6.

[0014] In a more optimized manner, the modified graphene B comprises the following raw materials, by mass parts: 10-15 parts carboxyl-activated graphene, 3-6 parts polyamide-polyether block copolymer, and 8-15 parts water; the modified nylon 6 comprises the following raw materials, by mass parts: 15-25 parts caprolactam, 0.5-1.5 parts 6-aminohexanoic acid, and 0.05-0.15 parts modified graphene B.

[0015] In a more optimized manner, the preparation of the polyamide-polyether block copolymer includes the following steps: under nitrogen protection, polyetheramine is added, the temperature is raised to 200-210°C, phosphorous acid is added, and the mixture is stirred at this temperature for 0.5-1 h. Nylon 66 salt is slowly added, and the temperature is raised to 220-230°C and reacted at this temperature for 2-4 h to obtain a polyetheramine-terminated polyamide prepolymer; adipic acid and phosphorous acid are added, the temperature is raised to 230-240°C, and the mixture is reacted for 3-4 h. The temperature is lowered to 210-220°C and a vacuum is applied. The temperature is raised to 230-240°C and reacted at this temperature for 1-2 h. The mixture is then cooled to obtain the polyamide-polyether block copolymer.

[0016] In a more optimized manner, the polyamide-polyether block copolymer comprises the following raw materials, in molar amounts: 1-2 mol polyetheramine, 0.8-1.5 mol nylon 66 salt, and 1-2 mol adipic acid; 0.8-1.5 wt% phosphorous acid is added to the polyetheramine-terminated polyamide prepolymer; and 0.3-0.8 wt% phosphorous acid is added to the polyamide-polyether block copolymer.

[0017] An optimized impregnation process is as follows: impregnation at 50~60℃ for 0.5~1h, with a bath ratio of 1:50~1:60.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0019] (1) This invention prepares carboxyl-activated graphene; firstly, carboxyl-activated graphene is reacted with tetralysine to obtain modified graphene A, and modified graphene A is combined with glutaraldehyde, ethanol, propanol and sodium carbonate to prepare an impregnation solution, which is used to impregnate and finish the modified nylon fibers obtained in subsequent steps; usually, when modifying nylon by adding graphene, there is a problem of poor graphene dispersion, so it is not advisable to add too much, and when using an impregnation solution containing graphene to modify nylon fibers, only the fiber surface can be modified, and the effect is not good; in order to achieve This invention achieves excellent performance by adding a small amount of modified graphene B to nylon while simultaneously preparing an impregnation solution containing modified graphene A to impregnate and modify the nylon fiber. This two-pronged approach modifies the nylon with graphene, resulting in high-performance graphene-modified nylon spun fibers. The addition of modified graphene A to the impregnation solution provides good strength and antibacterial properties. The added glutaraldehyde can crosslink with the amino groups in modified graphene A and the modified nylon fiber prepared in subsequent steps under the impregnation process specified in this invention, resulting in a tight bond between the two.

[0020] (2) Modified graphene B was prepared using carboxyl-activated graphene and polyamide-polyether block copolymer. Modified nylon 6 was prepared using caprolactam, 6-aminohexanoic acid, and modified graphene B. After melt spinning and subsequent drawing, modified nylon fiber was obtained. The modified nylon fiber contains amino groups, which can be crosslinked with the amino groups in the modified graphene A by glutaraldehyde, making the two tightly bonded. The modified graphene B incorporates polyamide-polyether block copolymer, which has good hydrophilicity. The polyamide-polyether block copolymer contains nylon. 66 salt, nylon 66 has good compatibility with nylon 6 and has a high elastic modulus. Therefore, this polyamide polyether block copolymer can improve the compatibility between graphene and nylon 6 (nylon), while improving its hydrophilicity and elastic modulus. When preparing modified nylon 6, controlling the amount of modified graphene B added avoids the problem of decreased mechanical properties of nylon due to poor graphene dispersion. At the same time, the combined use of modified graphene A and modified graphene B ensures that the obtained graphene nylon spun fibers have excellent properties. Detailed Implementation

[0021] The present invention will be further described below with reference to specific embodiments.

[0022] The following examples include the following raw materials: polyetheramine (ED600, Shandong Liyuan Guosheng Chemical Co., Ltd.); nylon 66 salt (Shenzhen Besute Technology Co., Ltd.); adipic acid (CAS: 124-04-9); phosphorous acid (CAS: 13598-36-2); caprolactam; 6-aminohexanoic acid (CAS: 60-32-2); carboxylated graphene (oxygen content >15wt%, number of layers <10 layers, Xi'an Qiyue Biotechnology Co., Ltd.); 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (CAS: 7084-11-9); tetralysine (CAS: 997-20-6); glutaraldehyde (CAS: 111-30-8); ethanol (CAS: 64-17-5); propanol (CAS: 71-23-8); sodium carbonate (CAS: 497-19-8).

[0023] The following quantities are by weight;

[0024] Example 1

[0025] S1: Take 5 parts of carboxylated graphene and water, prepare a dispersion of 1 mg / mL, sonicate for 1 h, then add 1.5 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, stir for 2 h to obtain carboxylated activated graphene; add 3 parts of tetralysine, heat to 130℃ and stir for 12 h, wash and dry to obtain modified graphene A;

[0026] S2: Under nitrogen protection, add 2 mol of polyetheramine, raise the temperature to 210℃, add 1 wt% of phosphorous acid, keep warm and stir for 1 h, slowly add 1 mol of nylon 66 salt, raise the temperature to 230℃ and keep the reaction for 3 h to obtain polyetheramine-terminated polyamide prepolymer; add 1.5 mol of adipic acid and 0.5 wt% phosphorous acid, raise the temperature to 238℃ and react for 4 h, lower the temperature to 220℃ and evacuate to a vacuum degree of -0.05 kPa, raise the temperature to 240℃ and keep the reaction for 2 h, cool to obtain polyamide-polyether block copolymer;

[0027] S3: Take 13 parts of carboxyl-activated graphene, 4 parts of polyamide-polyether block copolymer, and 12 parts of water, stir evenly, heat to 130℃ and stir for 12 hours, dry to obtain modified graphene B; Take 20 parts of caprolactam, 1 part of 6-aminohexanoic acid, and 0.01 parts of modified graphene B, turn on the reflux condenser, introduce nitrogen gas, heat to 255℃ to melt the above substances, stir for 7 hours to obtain modified nylon 6, and obtain modified nylon fiber through melt spinning and post-drawing; During melt spinning, the screw temperature is set as follows: Zone 1 temperature 290℃, Zones 2, 3, and 4 temperatures 320℃, melt transfer bend temperature 320℃, metering pump speed 30 R / min, temperature 320℃, and spinning speed 900 m / min; During post-drawing, the heat treatment temperature is 120℃, and 4 times post-drawing is performed;

[0028] S4: Take 10 parts modified graphene A, 1.5 parts glutaraldehyde, 630 parts ethanol, 70 parts propanol, and 1.5 parts sodium carbonate, stir evenly to obtain an impregnation solution, put the modified nylon fiber into the impregnation solution, impregnate at 60℃ for 1 hour, with a bath ratio of 1:60, take it out and dry to obtain graphene nylon spun fiber.

[0029] Example 2

[0030] S1: Take 5 parts of carboxylated graphene and water, prepare a dispersion of 1 mg / mL, sonicate for 1 h, then add 2 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, stir for 2 h to obtain carboxylated activated graphene; add 4 parts of tetralysine, heat to 130℃ and stir for 12 h, wash and dry to obtain modified graphene A;

[0031] S2: Under nitrogen protection, add 2 mol of polyetheramine, raise the temperature to 210℃, add 1 wt% of phosphorous acid, keep warm and stir for 1 h, slowly add 1.5 mol of nylon 66 salt, raise the temperature to 230℃ and keep the reaction for 3 h to obtain polyetheramine-terminated polyamide prepolymer; add 2 mol of adipic acid and 0.5 wt% phosphorous acid, raise the temperature to 238℃ and react for 4 h, lower the temperature to 220℃ and evacuate to a vacuum degree of -0.05 kPa, raise the temperature to 240℃ and keep the reaction for 2 h, cool to obtain polyamide-polyether block copolymer;

[0032] S3: Take 15 parts of carboxyl-activated graphene, 6 parts of polyamide-polyether block copolymer, and 12 parts of water, stir evenly, heat to 130℃ and stir for 12 hours, dry to obtain modified graphene B; Take 25 parts of caprolactam, 1.5 parts of 6-aminohexanoic acid, and 0.15 parts of modified graphene B, turn on the reflux condenser, introduce nitrogen gas, heat to 255℃ to melt the above substances, stir for 7 hours to obtain modified nylon 6, and obtain modified nylon fiber through melt spinning and post-drawing; During melt spinning, the screw temperature is set as follows: Zone 1 temperature 290℃, Zones 2, 3, and 4 temperatures 320℃, melt transfer bend temperature 320℃, metering pump speed 30 R / min, temperature 320℃, and spinning speed 900 m / min; During post-drawing, the heat treatment temperature is 120℃, and 4 times post-drawing is performed;

[0033] S4: Take 15 parts of modified graphene A, 1.5 parts of glutaraldehyde, 630 parts of ethanol, 70 parts of propanol, and 1.5 parts of sodium carbonate, stir evenly to obtain an impregnation solution, put the modified nylon fiber into the impregnation solution, impregnate at 60°C for 1 hour, with a bath ratio of 1:60, take it out and dry to obtain graphene nylon spun fiber.

[0034] Example 3

[0035] S1: Take 5 parts of carboxylated graphene and water, prepare a dispersion of 1 mg / mL, sonicate for 1 h, then add 1 part of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, stir for 2 h to obtain carboxylated activated graphene; add 2 parts of tetralysine, heat to 130℃ and stir for 12 h, wash and dry to obtain modified graphene A;

[0036] S2: Under nitrogen protection, add 1 mol of polyetheramine, raise the temperature to 210℃, add 1 wt% of phosphoric acid, keep warm and stir for 1 h, slowly add 0.8 mol of nylon 66 salt, raise the temperature to 230℃ and keep the reaction for 3 h to obtain polyetheramine-terminated polyamide prepolymer; add 1 mol of adipic acid and 0.5 wt% phosphoric acid, raise the temperature to 238℃ and react for 4 h, lower the temperature to 220℃ and evacuate to a vacuum degree of -0.05 kPa, raise the temperature to 240℃ and keep the reaction for 2 h, cool to obtain polyamide-polyether block copolymer;

[0037] S3: Take 10 parts of carboxyl-activated graphene, 3 parts of polyamide-polyether block copolymer, and 12 parts of water, stir evenly, heat to 130℃ and stir for 12 hours, dry to obtain modified graphene B; Take 15 parts of caprolactam, 0.5 parts of 6-aminohexanoic acid, and 0.05 parts of modified graphene B, turn on the reflux condenser, introduce nitrogen, heat to 255℃ to melt the above substances, stir for 7 hours to obtain modified nylon 6, and obtain modified nylon fiber through melt spinning and post-drawing; During melt spinning, the screw temperature is set as follows: Zone 1 temperature 290℃, Zones 2, 3, and 4 temperatures 320℃, melt transfer bend temperature 320℃, metering pump speed 30 R / min, temperature 320℃, and spinning speed 900 m / min; During post-drawing, the heat treatment temperature is 120℃, and 4 times post-drawing is performed;

[0038] S4: Take 9 parts of modified graphene A, 1.5 parts of glutaraldehyde, 630 parts of ethanol, 70 parts of propanol, and 1.5 parts of sodium carbonate, stir evenly to obtain an impregnation solution, put the modified nylon fiber into the impregnation solution, impregnate at 60°C for 1 hour, with a bath ratio of 1:60, take it out and dry to obtain graphene nylon spun fiber.

[0039] Comparative Example 1 (modified graphene A was replaced with amino graphene, and the remaining steps were the same as in Example 1): S1: Under nitrogen protection, 2 mol of polyetheramine was added, the temperature was raised to 210°C, 1 wt% of phosphoric acid was added, and the mixture was stirred for 1 h. 1 mol of nylon 66 salt was slowly added, the temperature was raised to 230°C and the reaction was maintained for 3 h to obtain polyetheramine-terminated polyamide prepolymer; 1.5 mol of adipic acid and 0.5 wt% phosphoric acid were added, the temperature was raised to 238°C and the reaction was maintained for 4 h. The temperature was lowered to 220°C and a vacuum was drawn with a vacuum degree of -0.05 kPa. The temperature was raised to 240°C and the reaction was maintained for 2 h. After cooling, a polyamide-polyether block copolymer was obtained.

[0040] S2: Take 13 parts of carboxyl-activated graphene, 4 parts of polyamide-polyether block copolymer, and 12 parts of water, stir evenly, heat to 130℃ and stir for 12 hours, dry to obtain modified graphene B; take 20 parts of caprolactam, 1 part of 6-aminohexanoic acid, and 0.01 parts of modified graphene B, turn on the reflux condenser, introduce nitrogen gas, heat to 255℃ to melt the above substances, stir for 7 hours to obtain modified nylon 6, and obtain modified nylon fiber through melt spinning and post-drawing; during melt spinning, the screw temperature is set as follows: zone 1 temperature 290℃, zone 2, zone 3, and zone 4 temperature 320℃, melt transfer bend temperature 320℃, metering pump speed 30 R / min, temperature 320℃, and spinning speed 900 m / min; during post-drawing, the heat treatment temperature is 120℃, and 4 times post-drawing is performed;

[0041] S3: Take 10 parts of amino graphene, 1.5 parts of glutaraldehyde, 630 parts of ethanol, 70 parts of propanol, and 1.5 parts of sodium carbonate, stir evenly to obtain an impregnation solution, put the modified nylon fiber into the impregnation solution, impregnate at 60°C for 1 hour, with a bath ratio of 1:60, take it out and dry to obtain graphene nylon spun fiber.

[0042] Comparative Example 2 (without introducing glutaraldehyde, the remaining methods and steps are the same as in Example 1): S1: Take 5 parts of carboxylated graphene and water, prepare a dispersion of 1 mg / mL, sonicate for 1 h, then add 1.5 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, stir for 2 h to obtain carboxylated activated graphene; add 3 parts of tetralysine, heat to 130℃ and stir for 12 h, wash and dry to obtain modified graphene A;

[0043] S2: Under nitrogen protection, add 2 mol of polyetheramine, raise the temperature to 210℃, add 1 wt% of phosphorous acid, keep warm and stir for 1 h, slowly add 1 mol of nylon 66 salt, raise the temperature to 230℃ and keep the reaction for 3 h to obtain polyetheramine-terminated polyamide prepolymer; add 1.5 mol of adipic acid and 0.5 wt% phosphorous acid, raise the temperature to 238℃ and react for 4 h, lower the temperature to 220℃ and evacuate to a vacuum degree of -0.05 kPa, raise the temperature to 240℃ and keep the reaction for 2 h, cool to obtain polyamide-polyether block copolymer;

[0044] S3: Take 13 parts of carboxyl-activated graphene, 4 parts of polyamide-polyether block copolymer, and 12 parts of water, stir evenly, heat to 130℃ and stir for 12 hours, dry to obtain modified graphene B; Take 20 parts of caprolactam, 1 part of 6-aminohexanoic acid, and 0.01 parts of modified graphene B, turn on the reflux condenser, introduce nitrogen gas, heat to 255℃ to melt the above substances, stir for 7 hours to obtain modified nylon 6, and obtain modified nylon fiber through melt spinning and post-drawing; During melt spinning, the screw temperature is set as follows: Zone 1 temperature 290℃, Zones 2, 3, and 4 temperatures 320℃, melt transfer bend temperature 320℃, metering pump speed 30 R / min, temperature 320℃, and spinning speed 900 m / min; During post-drawing, the heat treatment temperature is 120℃, and 4 times post-drawing is performed;

[0045] S4: Take 10 parts of modified graphene A, 630 parts of ethanol, 70 parts of propanol, and 1.5 parts of sodium carbonate, stir evenly to obtain an impregnation solution, put the modified nylon fiber into the impregnation solution, impregnate at 60℃ for 1 hour, with a bath ratio of 1:60, take it out and dry to obtain graphene nylon spun fiber.

[0046] Comparative Example 3 (modified graphene B was replaced with amino-based graphene, and the remaining steps were the same as in Example 1): S1: Take 5 parts of carboxylated graphene and water to prepare a dispersion of 1 mg / mL, sonicate for 1 h, then add 1.5 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, stir for 2 h to obtain carboxylated activated graphene; add 3 parts of tetralysine, heat to 130℃ and stir for 12 h, wash and dry to obtain modified graphene A;

[0047] S2: Take 20 parts caprolactam, 1 part 6-aminohexanoic acid, and 0.01 parts aminographene. Turn on the reflux condenser, introduce nitrogen gas, and heat to 255℃ to melt the above substances. Stir for 7 hours to obtain modified nylon 6. After melt spinning and post-drawing, obtain modified nylon fiber. During melt spinning, the screw temperature is set as follows: Zone 1 temperature 290℃, Zones 2, 3, and 4 temperatures 320℃, melt transfer bend temperature 320℃, metering pump speed 30 R / min, temperature 320℃, and spinning speed 900 m / min. During post-drawing, the heat treatment temperature is 120℃, and post-drawing is performed 4 times.

[0048] S3: Take 10 parts of modified graphene A, 1.5 parts of glutaraldehyde, 630 parts of ethanol, 70 parts of propanol, and 1.5 parts of sodium carbonate, stir evenly to obtain an impregnation solution, put the modified nylon fiber into the impregnation solution, impregnate at 60°C for 1 hour, with a bath ratio of 1:60, take it out and dry to obtain graphene nylon spun fiber.

[0049] Comparative Example 4 (with increased amount of modified graphene, the rest of the steps are the same as in Example 1): S1: Take 5 parts of carboxylated graphene and water, prepare a dispersion of 1 mg / mL, sonicate for 1 h, then add 1.5 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, stir for 2 h to obtain carboxylated activated graphene; add 3 parts of tetralysine, heat to 130℃ and stir for 12 h, wash and dry to obtain modified graphene A;

[0050] S2: Under nitrogen protection, add 2 mol of polyetheramine, raise the temperature to 210℃, add 1 wt% of phosphorous acid, keep warm and stir for 1 h, slowly add 1 mol of nylon 66 salt, raise the temperature to 230℃ and keep the reaction for 3 h to obtain polyetheramine-terminated polyamide prepolymer; add 1.5 mol of adipic acid and 0.5 wt% phosphorous acid, raise the temperature to 238℃ and react for 4 h, lower the temperature to 220℃ and evacuate to a vacuum degree of -0.05 kPa, raise the temperature to 240℃ and keep the reaction for 2 h, cool to obtain polyamide-polyether block copolymer;

[0051] S3: Take 13 parts of carboxyl-activated graphene, 4 parts of polyamide-polyether block copolymer, and 12 parts of water, stir evenly, heat to 130℃ and stir for 12 hours, dry to obtain modified graphene B; Take 20 parts of caprolactam, 1 part of 6-aminohexanoic acid, and 0.2 parts of modified graphene B, turn on the reflux condenser, introduce nitrogen gas, heat to 255℃ to melt the above substances, stir for 7 hours to obtain modified nylon 6, and obtain modified nylon fiber through melt spinning and post-drawing; During melt spinning, the screw temperature is set as follows: Zone 1 temperature 290℃, Zones 2, 3, and 4 temperatures 320℃, melt transfer bend temperature 320℃, metering pump speed 30 R / min, temperature 320℃, and spinning speed 900 m / min; During post-drawing, the heat treatment temperature is 120℃, and 4 times post-drawing is performed;

[0052] S4: Take 10 parts modified graphene A, 1.5 parts glutaraldehyde, 630 parts ethanol, 70 parts propanol, and 1.5 parts sodium carbonate, stir evenly to obtain an impregnation solution, put the modified nylon fiber into the impregnation solution, impregnate at 60℃ for 1 hour, with a bath ratio of 1:60, take it out and dry to obtain graphene nylon spun fiber.

[0053] Experiment: Graphene nylon spun fibers prepared in Examples 1-3 and Comparative Examples 1-4 were used; (1) their moisture regain over 60 minutes was tested according to GB / T9995-1997 and GB / T6529; (2) their antibacterial effect was tested according to GB / T20944.3-2008; (3) modified nylon 6 prepared in Examples 1-3 and Comparative Examples 1-4 was used to injection mold standard strips according to GB / T1703.1-2019, and its tensile strength was tested according to standard GB / T1040.1-2018; specific data are shown in Table 1.

[0054] Table 1 Test Results

[0055] Moisture regain / % Antibacterial rate / % Tensile strength / MPa Example 1 5.15 99.7 79 Example 2 5.10 99.5 79 Example 3 5.11 99.5 78 Comparative Example 1 4.57 75.2 72 Comparative Example 2 4.55 86.6 74 Comparative Example 3 4.39 92.4 71 Comparative Example 4 4.72 95.9 69

[0056] In Comparative Example 1, replacing modified graphene A with aminated graphene resulted in a decrease in the antibacterial properties of the graphene nylon spun fiber. In Comparative Example 2, the absence of glutaraldehyde led to inferior performance of the resulting graphene nylon spun fiber compared to the examples. In Comparative Example 3, replacing modified graphene B with aminated graphene resulted in a decrease in all properties of the graphene nylon spun fiber, with a significant decrease in hydrophilicity. In Comparative Example 4, increasing the amount of modified graphene B resulted in a decrease in tensile strength, possibly due to graphene agglomeration. In summary, this invention provides a graphene nylon spun fiber with good antibacterial and hydrophilic properties, high strength, excellent performance, and wide applicability, as well as its preparation method.

[0057] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0058] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A process for preparing graphene-nylon spun fibers, characterized in that, Includes the following steps: S1: Modified graphene A was prepared by taking carboxyl-activated graphene and polylysine. S2: Take carboxyl-activated graphene, polyamide-polyether block copolymer, and water, stir evenly, heat to 120~140℃ and stir for 10~14h, dry to obtain modified graphene B; Take caprolactam, 6-aminohexanoic acid, and modified graphene B, turn on the reflux condenser, introduce nitrogen gas, heat to 250~260℃, stir for 6~7h to obtain modified nylon 6, and then melt spin and stretch to obtain modified nylon fiber; S3: Take modified graphene A, glutaraldehyde, ethanol, propanol and sodium carbonate, stir evenly to obtain impregnation solution, put the modified nylon fiber into the impregnation solution, impregnate, take it out and dry to obtain graphene nylon spun fiber. The modified graphene B comprises the following raw materials, by mass parts: 10-15 parts carboxyl-activated graphene, 3-6 parts polyamide-polyether block copolymer, and 8-15 parts water; The modified nylon 6 comprises the following raw materials, by mass parts: 15-25 parts caprolactam, 0.5-1.5 parts 6-aminocaproic acid, and 0.05-0.15 parts modified graphene B; The preparation of the polyamide-polyether block copolymer includes the following steps: under nitrogen protection, the polyetheramine is heated to 200-210°C, phosphorous acid is added, and the mixture is stirred for 0.5-1 h. Nylon 66 salt is slowly added, and the mixture is heated to 220-230°C and reacted for 2-4 h to obtain a polyetheramine-terminated polyamide prepolymer. Adipic acid and phosphorous acid are added, the mixture is heated to 230-240°C, and reacted for 3-4 h. The mixture is then cooled to 210-220°C, vacuumed, heated to 230-240°C, and reacted for 1-2 h. After cooling, the polyamide-polyether block copolymer is obtained.

2. The preparation process of graphene nylon spun fiber according to claim 1, characterized in that, The impregnation solution comprises the following raw materials: 5-15 parts modified graphene A, 1-2 parts glutaraldehyde, 600-700 parts ethanol, 50-100 parts propanol, and 1-2 parts sodium carbonate.

3. The preparation process of graphene nylon spun fiber according to claim 1, characterized in that, The preparation of the modified graphene A includes the following steps: taking carboxylated graphene and water, ultrasonically dispersing for 1-2 hours to obtain a dispersion, adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, stirring for 1-2 hours to obtain carboxylated activated graphene; adding tetralysine, heating to 120-140℃ and stirring for 10-14 hours, washing and drying to obtain modified graphene A.

4. The preparation process of graphene nylon spun fiber according to claim 3, characterized in that, The modified graphene A comprises the following raw materials, by mass parts: 3-6 parts carboxylated graphene, 1-2 parts 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 2-4 parts polylysine; the concentration of the dispersion is 1 mg / mL.

5. The preparation process of graphene nylon spun fiber according to claim 1, characterized in that, The polyamide-polyether block copolymer comprises the following raw materials, in molar amounts: 1-2 mol polyetheramine, 0.8-1.5 mol nylon 66 salt, and 1-2 mol adipic acid; 0.8-1.5 wt% phosphorous acid is added to the polyetheramine-terminated polyamide prepolymer; and 0.3-0.8 wt% phosphorous acid is added to the polyamide-polyether block copolymer.

6. The preparation process of graphene nylon spun fiber according to claim 1, characterized in that, The impregnation process is as follows: impregnation at 50~60℃ for 0.5~1h, with a liquor ratio of 1:50~1:

60.

7. Graphene nylon spun fiber obtained by the preparation process of graphene nylon spun fiber according to any one of claims 1 to 6.