Preparation method of antibacterial modified polyester hollow fiber

Abstract

The invention relates to the technical field of polyester fibers, and discloses a preparation method of antibacterial modified polyester hollow fibers, which comprises the following steps: by taking nitrilotriacetic acid, thionyl chloride, epoxy chloropropane, eugenol and the like as raw materials, carrying out acylating chlorination reaction, quaternization reaction and esterification reaction to obtain eugenol epoxy quaternary ammonium salt. The preparation method comprises the following steps: carrying out ring-opening reaction on carboxyl groups in graphene oxide and epoxy groups in eugenol epoxy quaternary ammonium salt to obtain modified graphene, uniformly mixing the modified graphene with polyethylene glycol terephthalate, and carrying out a series of steps to finally obtain the antibacterial modified polyester hollow fiber. Eugenol and quaternary ammonium salt are utilized to improve the antibacterial property of the polyester hollow fiber, and graphene is utilized to improve the mechanical property of the polyester hollow fiber. The polyester hollow fiber prepared by the invention has excellent mechanical properties and antibacterial properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyester fibers, in particular to a preparation method of antibacterial modified polyester hollow fibers. BACKGROUND

[0002] Hollow fiber is an important profiled fiber, and its raw materials include polyester, nylon, viscose, etc. It has good warmth retention and loftiness, and is widely used in the fields of clothing, membrane separation materials, medical materials, etc. However, with the rapid development of science and technology and the continuous improvement of people's living standards, the practical function of clothing cannot meet the functional needs of consumers, and high-performance and multi-functional fiber products need to be developed.

[0003] Eugenol is an important bioactive compound extracted from natural cloves, which has the effects of anticancer, antioxidant, antiseptic, and antidepressant, and has broad-spectrum antibacterial and antifungal properties. Graphene has excellent optical properties, mechanical properties, toughness, etc., and is widely used in mobile devices, aerospace, new energy, etc. However, the structure of graphene is regular and does not contain any active groups, so its affinity to most polymer materials is greatly reduced and it is prone to aggregation, which causes certain difficulties in the processing and molding of polymer materials. Therefore, functional chemical modification of graphene is needed to make it well dispersed in the polymer material matrix and inhibit its own aggregation. SUMMARY

[0004] The present application aims to overcome the shortcomings of the prior art and provide a preparation method of antibacterial modified polyester hollow fibers, which has excellent antibacterial properties and mechanical properties.

[0005] To achieve the above-mentioned purpose, the technical solution adopted by the present application is as follows: a preparation method of antibacterial modified polyester hollow fibers, the preparation method is as follows: (1) Add graphene oxide to deionized water and ultrasonically disperse, then add eugenol-based epoxy quaternary ammonium salt to it, control the temperature to be 60-70℃, stir for 8-12h, after the reaction is completed, centrifuge, wash with deionized water, and dry to obtain modified graphene; (2) Mix the dried modified graphene with polyethylene terephthalate uniformly, add it to an extruder, plasticize and melt, then enter a spinning box through a spinning assembly, wind after cooling, and stretch to obtain antibacterial modified polyester hollow fibers.

[0006] Further preferably, in the step (1), the amount of graphene oxide and eugenol-based epoxy quaternary ammonium salt is 100g: (150-250) g.

[0007] Further preferably, in the (2), the amount ratio of the modified graphene and the polyethylene terephthalate is (0.5-2.5) g:100 g.

[0008] Further preferably, in the (2), the spinning temperature is 285℃; the ring blowing air speed is 3.4 m / s, the ring blowing temperature is 22℃; the drawing temperature is 65℃, and the drawing multiple is 2.80.

[0009] Further preferably, in the (1), the preparation method of the eugenol epoxy quaternary ammonium salt is as follows: S1, nitrilotriacetic acid is added to xylene, stirred and dissolved, then thionyl chloride is added, heated to 50-60℃, refluxed for 2-4h, after the reaction is completed, the temperature is reduced to room temperature, and distilled under reduced pressure to obtain nitrilotriacetyl chloride; S2, nitrilotriacetyl chloride and epichlorohydrin are added to methanol, stirred and dispersed, heated to 50-55℃, reacted for 8-12h, after the reaction is completed, the temperature is reduced to room temperature, rotary evaporated, washed with diethyl ether, and dried to obtain a triacetyl chloride epoxy quaternary ammonium salt; S3, eugenol and triethylamine are added to xylene, stirred and dissolved, then the triacetyl chloride epoxy quaternary ammonium salt is added, stirred at room temperature for 20-36h, after the reaction is completed, filtered, and distilled under reduced pressure to obtain an eugenol epoxy quaternary ammonium salt.

[0010] Further preferably, in the S1, the amount ratio of nitrilotriacetic acid and thionyl chloride is 1 mol:(3-3.5) mol.

[0011] Further preferably, in the S2, the amount ratio of nitrilotriacetyl chloride and epichlorohydrin is 1 mol:(1-1.4) mol.

[0012] Further preferably, in the S3, the amount ratio of eugenol, triethylamine and triacetyl chloride epoxy quaternary ammonium salt is (3-3.4) mol:(3-3.6) mol:1 mol.

[0013] Compared with the prior art, the present application has the following beneficial effects: The present application uses nitrilotriacetic acid, thionyl chloride, epichlorohydrin, eugenol and the like as raw materials, and through acyl chloride reaction, quaternary ammonium reaction and esterification reaction, an eugenol epoxy quaternary ammonium salt is obtained, which has a novel structure and a simple preparation method. The carboxyl group in the graphene oxide and the epoxy group in the eugenol epoxy quaternary ammonium salt are used to carry out ring-opening reaction to obtain modified graphene, which is then mixed uniformly with polyethylene terephthalate, plasticized and melted, extruded from a silk hole, wound after cooling, drawn, and finally an antibacterial modified polyester hollow fiber is obtained.

[0014] The graphene used in the application is easy to agglomerate, the organic modification of the graphene in the application increases the compatibility of the graphene with the polymer material, reduces the agglomeration degree, and the graphene can be uniformly dispersed in the fiber, and when subjected to external force, the graphene can absorb more energy as a stress concentration point, so that the fiber is not easy to break, and the mechanical properties of the polyester hollow fiber are improved.

[0015] The eugenol used in the application is a natural antibacterial substance, but the eugenol is easy to volatilize in the application process and has low utilization rate, the eugenol is reacted with the triacetyl chloride epoxy quaternary ammonium salt to reduce the volatilization performance and improve the utilization rate, and the quaternary ammonium salt also has antibacterial effect, and the two mutually assist each other to improve the antibacterial performance of the polyester hollow fiber. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 is a reaction route of the eugenol-based epoxy quaternary ammonium salt. DETAILED DESCRIPTION

[0017] The high-adhesion stone coating and the preparation method thereof will be further described in combination with some specific embodiments. The specific embodiments are used to further illustrate the application, but do not limit the protection scope of the application.

[0018] Example 1 (1) 0.1 mol of nitrilotriacetic acid is added to xylene, stirred and dissolved, 0.3 mol of thionyl chloride is then added, the temperature is raised to 55 DEG C, and refluxed for 3 h, after the reaction is completed, the temperature is lowered to room temperature, and reduced pressure distillation is performed to obtain nitrilotriacetyl chloride.

[0019] (2) 0.15 mol of nitrilotriacetyl chloride and 0.18 mol of epichlorohydrin are added to methanol, stirred and dispersed, the temperature is raised to 55 DEG C, and reacted for 10 h, after the reaction is completed, the temperature is lowered to room temperature, rotary evaporation is performed, washed with diethyl ether, and dried to obtain triacetyl chloride epoxy quaternary ammonium salt.

[0020] (3) 0.34 mol of eugenol and 0.3 mol of triethylamine are added to xylene, stirred and dissolved, 0.1 mol of triacetyl chloride epoxy quaternary ammonium salt is then added, stirred at room temperature for 30 h, after the reaction is completed, filtration is performed, and reduced pressure distillation is performed to obtain eugenol-based epoxy quaternary ammonium salt.

[0021] (4) 10 g of graphene oxide is added to deionized water, ultrasonic dispersion is performed, 15 g of eugenol-based epoxy quaternary ammonium salt is then added, the temperature is controlled at 60 DEG C, and stirred for 12 h, after the reaction is completed, centrifugation is performed, washed with deionized water, and dried to obtain modified graphene.

[0022] (5) 0.5 g of the dried modified graphene was uniformly mixed with 100 g of polyethylene terephthalate, added to an extruder, plasticized and melted, and then introduced into a spinning box through a spinneret assembly for extrusion, and after cooling, wound and stretched, wherein the spinning temperature was 285°C, the ring blowing air speed was 3.4 m / s, the ring blowing temperature was 22°C, the stretching temperature was 65°C, and the stretching multiple was 2.80, to obtain the antibacterial modified polyester hollow fiber.

[0023] Example 2 (1) 0.1 mol of nitrilotriacetic acid was added to xylene, stirred and dissolved, and then 0.35 mol of thionyl chloride was added thereto, and the temperature was raised to 50°C, and refluxed for 4 h. After the reaction was completed, the temperature was lowered to room temperature, and distilled under reduced pressure to obtain nitrilotriacetyl chloride.

[0024] (2) 0.15 mol of nitrilotriacetyl chloride and 0.2 mol of epichlorohydrin were added to methanol, stirred and dispersed, and the temperature was raised to 55°C, and reacted for 8 h. After the reaction was completed, the temperature was lowered to room temperature, and rotary evaporation was performed, and then washed with diethyl ether and dried to obtain a triacetyl chloride-based epoxy quaternary ammonium salt.

[0025] (3) 0.34 mol of eugenol and 0.35 mol of triethylamine were added to xylene, stirred and dissolved, and then 0.1 mol of the triacetyl chloride-based epoxy quaternary ammonium salt was added thereto, and stirred at room temperature for 24 h. After the reaction was completed, filtration was performed, and then distilled under reduced pressure to obtain an eugenol-based epoxy quaternary ammonium salt.

[0026] (4) 10 g of graphene oxide was added to deionized water, and ultrasonically dispersed, and then 18 g of the eugenol-based epoxy quaternary ammonium salt was added thereto, and the temperature was controlled at 70°C, and stirred for 10 h. After the reaction was completed, centrifugation was performed, and then washed with deionized water and dried to obtain modified graphene.

[0027] (5) 1 g of the dried modified graphene was uniformly mixed with 100 g of polyethylene terephthalate, added to an extruder, plasticized and melted, and then introduced into a spinning box through a spinneret assembly for extrusion, and after cooling, wound and stretched, wherein the spinning temperature was 285°C, the ring blowing air speed was 3.4 m / s, the ring blowing temperature was 22°C, the stretching temperature was 65°C, and the stretching multiple was 2.80, to obtain the antibacterial modified polyester hollow fiber.

[0028] Example 3 (1) 0.1 mol of nitrilotriacetic acid was added to xylene, stirred and dissolved, and then 0.35 mol of thionyl chloride was added thereto, and the temperature was raised to 60°C, and refluxed for 2 h. After the reaction was completed, the temperature was lowered to room temperature, and distilled under reduced pressure to obtain nitrilotriacetyl chloride.

[0029] (2) 0.15 mol of nitrilo triacetyl chloride and 0.15 mol of epichlorohydrin were added to methanol, stirred and dispersed, heated to 55°C, reacted for 12 h, after the reaction was completed, the temperature was lowered to room temperature, rotary evaporation was performed, washed with diethyl ether, and dried to obtain a triacetyl chloride epoxy quaternary ammonium salt.

[0030] (3) 0.34 mol of eugenol and 0.36 mol of triethylamine were added to xylene, stirred and dissolved, 0.1 mol of triacetyl chloride epoxy quaternary ammonium salt was added thereto, stirred at room temperature for 20 h, after the reaction was completed, filtration was performed, and vacuum distillation was performed to obtain an eugenol epoxy quaternary ammonium salt.

[0031] (4) 10 g of graphene oxide was added to deionized water, ultrasonically dispersed, 20 g of eugenol epoxy quaternary ammonium salt was added thereto, the temperature was controlled at 65°C, and stirred for 8 h, after the reaction was completed, centrifugation was performed, washed with deionized water, and dried to obtain modified graphene.

[0032] (5) 1.5 g of dried modified graphene was uniformly mixed with 100 g of polyethylene terephthalate, added to an extruder, plasticized and melted, and then introduced into a spinning box through a spinneret assembly, wound after cooling, and stretched, wherein the spinning temperature was 285°C, the ring blowing air speed was 3.4 m / s, the ring blowing temperature was 22°C, the stretching temperature was 65°C, and the stretching ratio was 2.80, to obtain an antibacterial modified polyester hollow fiber.

[0033] Example 4 (1) 0.1 mol of nitrilo triacetic acid was added to xylene, stirred and dissolved, 0.34 mol of thionyl chloride was added thereto, heated to 60°C, and refluxed for 3 h, after the reaction was completed, the temperature was lowered to room temperature, and vacuum distillation was performed to obtain nitrilo triacetyl chloride.

[0034] (2) 0.15 mol of nitrilo triacetyl chloride and 0.2 mol of epichlorohydrin were added to methanol, stirred and dispersed, heated to 50°C, reacted for 10 h, after the reaction was completed, the temperature was lowered to room temperature, rotary evaporation was performed, washed with diethyl ether, and dried to obtain a triacetyl chloride epoxy quaternary ammonium salt.

[0035] (3) 0.32 mol of eugenol and 0.3 mol of triethylamine were added to xylene, stirred and dissolved, 0.1 mol of triacetyl chloride epoxy quaternary ammonium salt was added thereto, stirred at room temperature for 24 h, after the reaction was completed, filtration was performed, and vacuum distillation was performed to obtain an eugenol epoxy quaternary ammonium salt.

[0036] (4) 10 g of graphene oxide was added to deionized water and ultrasonically dispersed, 23 g of eugenol epoxy quaternary ammonium salt was then added thereto, the temperature was controlled at 65°C, and stirring was performed for 10 h. After the reaction was completed, centrifugation, deionized water washing, and drying were performed to obtain modified graphene.

[0037] (5) 2 g of dried modified graphene was uniformly mixed with 100 g of polyethylene terephthalate, and then added to an extruder, plasticized and melted, and then extruded through a spinning pack assembly into a spinning box, wound after cooling, and stretched, wherein the spinning temperature was 285°C, the ring blowing air speed was 3.4 m / s, the ring blowing temperature was 22°C, the stretching temperature was 65°C, and the stretching multiple was 2.80, to obtain an antibacterial modified polyester hollow fiber.

[0038] Example 5 (1) 0.1 mol of nitrilotriacetic acid was added to xylene and dissolved by stirring, 0.34 mol of thionyl chloride was then added thereto, the temperature was raised to 55°C, and refluxing was performed for 4 h. After the reaction was completed, the temperature was lowered to room temperature, and distillation was performed under reduced pressure to obtain nitrilotriacetyl chloride.

[0039] (2) 0.15 mol of nitrilotriacetyl chloride and 0.21 mol of epichlorohydrin were added to methanol and dispersed by stirring, the temperature was raised to 55°C, and reaction was performed for 8 h. After the reaction was completed, the temperature was lowered to room temperature, rotary evaporation was performed, and ether washing and drying were performed to obtain a triacetyl chloride epoxy quaternary ammonium salt.

[0040] (3) 0.3 mol of eugenol and 0.32 mol of triethylamine were added to xylene and dissolved by stirring, 0.1 mol of triacetyl chloride epoxy quaternary ammonium salt was then added thereto, and stirring was performed at room temperature for 36 h. After the reaction was completed, filtration was performed, and distillation was performed under reduced pressure to obtain an eugenol epoxy quaternary ammonium salt.

[0041] (4) 10 g of graphene oxide was added to deionized water and ultrasonically dispersed, 25 g of eugenol epoxy quaternary ammonium salt was then added thereto, the temperature was controlled at 65°C, and stirring was performed for 10 h. After the reaction was completed, centrifugation, deionized water washing, and drying were performed to obtain modified graphene.

[0042] (5) 2.5 g of dried modified graphene was uniformly mixed with 100 g of polyethylene terephthalate, and then added to an extruder, plasticized and melted, and then extruded through a spinning pack assembly into a spinning box, wound after cooling, and stretched, wherein the spinning temperature was 285°C, the ring blowing air speed was 3.4 m / s, the ring blowing temperature was 22°C, the stretching temperature was 65°C, and the stretching multiple was 2.80, to obtain an antibacterial modified polyester hollow fiber.

[0043] Comparative Example 1 The preparation method of the polyester hollow fiber provided by the present comparative example is basically the same as that of example 1, and the main difference is that graphene is used instead of modified graphene in step (5).

[0044] Comparative example 2 The preparation method of the polyester hollow fiber provided by the present comparative example is basically the same as that of example 1, and the main difference is that eugenol-based epoxy quaternary ammonium salt is used instead of modified graphene in step (5).

[0045] According to GB / T20944.3-2008, the antibacterial performance of the polyester hollow fiber is tested, and the test bacteria are Staphylococcus aureus and Escherichia coli.

[0046] Table 1: As can be seen from the table, the polyester hollow fiber prepared by the present application has good antibacterial performance, and the antibacterial rate can reach 99.9%.

[0047] The electronic single fiber strength tester is used to test the mechanical properties of the polyester hollow fiber.

[0048] Table 2: As can be seen from the table, the polyester hollow fiber prepared by the present application has good breaking strength, and the breaking strength can reach 5.08 cN / dtex.

[0049] For any person skilled in the art, many possible changes and modifications, or equivalent embodiments of the technical solutions of the present application can be made without departing from the scope of the technical solutions of the present application, by using the technical content disclosed above. Therefore, any simple modification, equivalent change and modification of the above examples made according to the technical essence of the present application, without departing from the content of the technical solutions of the present application, should still belong to the scope of protection of the technical solutions of the present application.

Claims

1. A method for preparing antibacterial modified polyester hollow fiber, characterized in that: The preparation method is as follows: (1) Adding graphene oxide to deionized water, ultrasonically dispersing, then adding eugenol-based epoxy quaternary ammonium salt, controlling the temperature to 60-70 ° C, stirring and reacting for 8-12 hours, after the reaction is completed, centrifuging, washing with deionized water, and drying to obtain modified graphene; (2) The dried modified graphene and polyethylene terephthalate are mixed evenly, added into an extruder, plasticized and melted, and then enter the spinning manifold to be extruded through the spinneret assembly. After cooling, the fibers are wound and stretched to obtain antibacterial modified polyester hollow fibers.

2. The method for preparing the antibacterial modified polyester hollow fiber according to claim 1, characterized in that: In the above (1), the usage ratio of graphene oxide and eugenol-based epoxy quaternary ammonium salt is 100 g: (150-250) g.

3. The method for preparing the antibacterial modified polyester hollow fiber according to claim 1, characterized in that: In the above (2), the usage ratio of modified graphene and polyethylene terephthalate is (0.5-2.5) g:100 g.

4. The method for preparing the antibacterial modified polyester hollow fiber according to claim 1, characterized in that: In the above (2), the spinning temperature is 285°C; the annular blowing speed is 3.4 m / s, and the annular blowing temperature is 22°C; the stretching temperature is 65°C, and the stretching ratio is 2.

80.

5. The method for preparing the antibacterial modified polyester hollow fiber according to claim 1, characterized in that: In (1), the preparation method of eugenol-based epoxy quaternary ammonium salt is: S1. Add nitrilotriacetic acid to xylene, stir and dissolve, then add thionyl chloride, raise the temperature to 50-60°C, reflux for 2-4 hours, cool to room temperature, and distill under reduced pressure to obtain nitrilotriacetyl chloride; S2, adding nitrilotriacetyl chloride and epichlorohydrin to methanol, stirring and dispersing, heating to 50-55 ° C, reacting for 8-12 hours, and cooling to room temperature after the reaction, rotary evaporation, washing with ether, and drying to obtain triacetyl chloride epoxy quaternary ammonium salt; S3. Add eugenol and triethylamine to xylene, stir to dissolve, then add triacetyl chloride epoxy quaternary ammonium salt thereto, stir and react at room temperature for 20-36 hours. After the reaction is completed, filter and distill under reduced pressure to obtain eugenol epoxy quaternary ammonium salt.

6. The method for preparing the antibacterial modified polyester hollow fiber according to claim 5, characterized in that: In the S1, the usage ratio of nitrilotriacetic acid and thionyl chloride is 1 mol: (3-3.5) mol.

7. The method for preparing the antibacterial modified polyester hollow fiber according to claim 5, characterized in that: In the above-mentioned S2, the usage ratio of nitrilotriacetyl chloride and epichlorohydrin is 1 mol:(1-1.4) mol.

8. The method for preparing the antibacterial modified polyester hollow fiber according to claim 5, characterized in that: In the above-mentioned S3, the usage ratio of eugenol, triethylamine and triacetyl chloride epoxy quaternary ammonium salt is (3-3.4) mol: (3-3.6) mol: 1 mol.

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