Preparation method of antibacterial modified polyester hollow fiber

Abstract

The application relates to the technical field of polyester fibers, and discloses a preparation method of antibacterial modified polyester hollow fibers; the preparation method takes nitrilotriacetic acid, chlorosulfoxide, epoxy chloropropane, eugenol and the like as raw materials, and obtains eugenol epoxy quaternary ammonium salt through acyl chloride reaction, quaternary ammonium reaction and esterification. The carboxyl groups in graphene oxide and the epoxy groups in eugenol epoxy quaternary ammonium salt are used to carry out ring-opening reaction, so that modified graphene is obtained; the modified graphene is uniformly mixed with polyethylene terephthalate, and through a series of steps, finally, the antibacterial modified polyester hollow fibers are obtained. The eugenol and quaternary ammonium salt are used to improve the antibacterial performance of the polyester hollow fibers, and the graphene is used to improve the mechanical performance of the polyester hollow fibers. The polyester hollow fibers prepared by the method have excellent mechanical performance and antibacterial performance.

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 fibers are 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 clothing, membrane separation materials, medical materials and other fields. 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 and other fields. 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. The prepared polyester hollow fibers have 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:

[0006] (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;

[0007] (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.

[0008] Further preferably, in the step (1), the amount of graphene oxide and eugenol-based epoxy quaternary ammonium salt is 100g: (150-250) g.

[0009] Further preferably, in the (2), the amount ratio of the modified graphene and the polyethylene terephthalate is (0.5-2.5) g:100 g.

[0010] Further preferably, in the (2), the spinning temperature is 285℃; the air blowing speed of the ring blowing is 3.4 m / s, and the ring blowing temperature is 22℃; the drawing temperature is 65℃, and the drawing multiple is 2.80.

[0011] Further preferably, in the (1), the preparation method of the eugenol-based epoxy quaternary ammonium salt is as follows:

[0012] S1, nitrilotriacetic acid is added to xylene, stirred and dissolved, then thionyl chloride is added thereto, 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;

[0013] 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-based epoxy quaternary ammonium salt;

[0014] S3, eugenol and triethylamine are added to xylene, stirred and dissolved, then the triacetyl chloride-based epoxy quaternary ammonium salt is added thereto, stirred at room temperature for 20-36h, after the reaction is completed, filtered, and distilled under reduced pressure to obtain an eugenol-based epoxy quaternary ammonium salt.

[0015] Further preferably, in the S1, the amount ratio of nitrilotriacetic acid and thionyl chloride is 1 mol:(3-3.5) mol.

[0016] Further preferably, in the S2, the amount ratio of nitrilotriacetyl chloride and epichlorohydrin is 1 mol:(1-1.4) mol.

[0017] Further preferably, in the S3, the amount ratio of eugenol, triethylamine and triacetyl chloride-based epoxy quaternary ammonium salt is (3-3.4) mol:(3-3.6) mol:1 mol.

[0018] Compared with the prior art, the present application has the following beneficial effects:

[0019] The present application takes nitrilotriacetic acid, chlorosulfoxide, epichlorohydrin, eugenol and the like as raw materials, and obtains eugenol epoxy quaternary ammonium salt through acyl chloride reaction, quaternary ammonization reaction and esterification, which has novel structure and simple preparation method. The carboxyl group in graphene oxide and the epoxy group in eugenol epoxy quaternary ammonium salt are used to carry out ring-opening reaction to obtain modified graphene, which is then mixed with polyethylene terephthalate, plasticized and fused, extruded from a silk hole, wound after cooling, stretched, and finally an antibacterial modified polyester hollow fiber is obtained.

[0020] The graphene used in the present application is prone to agglomeration, and the present application increases its compatibility with high polymer materials by organicization, reduces the agglomeration degree, and can be uniformly dispersed in the fiber, which can act as a stress concentration point to absorb more energy when subjected to external force, so that the fiber is not easy to break, thereby improving the mechanical properties of the polyester hollow fiber.

[0021] The eugenol used in the present application is a natural antibacterial substance, but it is prone to volatilization in the application process and has low utilization rate. The present application reacts it with triacetyl chloride epoxy quaternary ammonium salt to reduce the volatilization performance and improve the utilization rate. 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. The polyester hollow fiber prepared by the present application has excellent mechanical properties and antibacterial properties. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 is the reaction route of eugenol epoxy quaternary ammonium salt. DETAILED DESCRIPTION

[0023] The high-adhesion stone coating and the preparation method thereof will be further described below in combination with some specific embodiments. The specific embodiments are further used to illustrate the present application, but do not limit the protection scope of the present application.

[0024] Example 1

[0025] (1) 0.1 mol of nitrilotriacetic acid is added to xylene, stirred and dissolved, and then 0.3 mol of chlorosulfoxide is added thereto, heated to 55℃, and refluxed for 3 h. After the reaction is completed, the temperature is reduced to room temperature, and vacuum distillation is performed to obtain nitrilotriacetyl chloride.

[0026] (2) 0.15 mol of nitrilotriacetyl chloride and 0.18 mol of epichlorohydrin are added to methanol, stirred and dispersed, heated to 55℃, and reacted for 10 h. After the reaction is completed, the temperature is reduced to room temperature, rotary evaporation is performed, washed with diethyl ether, and dried to obtain triacetyl chloride epoxy quaternary ammonium salt.

[0027] (3) 0.34 mol of eugenol, 0.3 mol of triethylamine were added into xylene, stirred and dissolved, then 0.1 mol of triacetyl chloride epoxy quaternary ammonium salt was added, stirred at room temperature for 30 h, after the reaction was completed, filtration, reduced pressure distillation, eugenol epoxy quaternary ammonium salt was obtained.

[0028] (4) 10 g of graphene oxide was added into deionized water, ultrasonic dispersion, then 15 g of eugenol epoxy quaternary ammonium salt was added, the temperature was controlled at 60 ℃, stirred for 12 h, after the reaction was completed, centrifugation, deionized water washing, drying, modified graphene was obtained.

[0029] (5) 0.5 g of dried modified graphene was uniformly mixed with 100 g of polyethylene terephthalate, added into an extruder, plasticized and melted, then entered a spinning box through a spinning assembly, after cooling, winding, drawing, the spinning temperature was 285 ℃, the ring blowing air speed was 3.4 m / s, the ring blowing temperature was 22 ℃, the drawing temperature was 65 ℃, the drawing multiple was 2.80, an antibacterial modified polyester hollow fiber was obtained.

[0030] Example 2

[0031] (1) 0.1 mol of nitrilotriacetic acid was added into xylene, stirred and dissolved, then 0.35 mol of thionyl chloride was added, heated to 50 ℃, refluxed for 4 h, after the reaction was completed, reduced to room temperature, reduced pressure distillation, nitrilotriacetyl chloride was obtained.

[0032] (2) 0.15 mol of nitrilotriacetyl chloride, 0.2 mol of epichlorohydrin was added into methanol, stirred and dispersed, heated to 55 ℃, reacted for 8 h, after the reaction was completed, reduced to room temperature, rotary evaporation, ether washing, drying, triacetyl chloride epoxy quaternary ammonium salt was obtained.

[0033] (3) 0.34 mol of eugenol, 0.35 mol of triethylamine were added into xylene, stirred and dissolved, then 0.1 mol of triacetyl chloride epoxy quaternary ammonium salt was added, stirred at room temperature for 24 h, after the reaction was completed, filtration, reduced pressure distillation, eugenol epoxy quaternary ammonium salt was obtained.

[0034] (4) 10 g of graphene oxide was added into deionized water, ultrasonic dispersion, then 18 g of eugenol epoxy quaternary ammonium salt was added, the temperature was controlled at 70 ℃, stirred for 10 h, after the reaction was completed, centrifugation, deionized water washing, drying, modified graphene was obtained.

[0035] (5) 1 g of the dried modified graphene is uniformly mixed with 100 g of polyethylene terephthalate, added to an extruder, plasticized and melted, and then introduced into a spinning box through a spinning assembly for extrusion, after cooling, wound and stretched, wherein the spinning temperature is 285°C, the air blowing speed of the ring blowing is 3.4 m / s, the ring blowing temperature is 22°C, the stretching temperature is 65°C, and the stretching multiple is 2.80, to obtain the antibacterial modified polyester hollow fiber.

[0036] Example 3

[0037] (1) 0.1 mol of nitrilotriacetic acid is added to xylene, stirred and dissolved, 0.34 mol of thionyl chloride is added, heated to 60°C, refluxed for 3 h, cooled to room temperature, and distilled under reduced pressure to obtain nitrilotriacetyl chloride.

[0038] (2) 0.15 mol of nitrilotriacetyl chloride and 0.15 mol of epichlorohydrin are added to methanol, stirred and dispersed, heated to 55°C, reacted for 12 h, cooled to room temperature, rotary evaporated, washed with diethyl ether, and dried to obtain a triacetyl chloride epoxy quaternary ammonium salt.

[0039] (3) 0.34 mol of eugenol and 0.36 mol of triethylamine are added to xylene, stirred and dissolved, 0.1 mol of triacetyl chloride epoxy quaternary ammonium salt is added, stirred at room temperature for 20 h, filtered after the reaction is completed, and distilled under reduced pressure to obtain eugenol epoxy quaternary ammonium salt.

[0040] (4) 10 g of graphene oxide is added to deionized water, ultrasonically dispersed, 20 g of eugenol epoxy quaternary ammonium salt is added, the temperature is controlled at 65°C, and stirred for 8 h, after the reaction is completed, centrifuged, washed with deionized water, and dried to obtain modified graphene.

[0041] (5) 1.5 g of the dried modified graphene is uniformly mixed with 100 g of polyethylene terephthalate, added to an extruder, plasticized and melted, and then introduced into a spinning box through a spinning assembly for extrusion, after cooling, wound and stretched, wherein the spinning temperature is 285°C, the air blowing speed of the ring blowing is 3.4 m / s, the ring blowing temperature is 22°C, the stretching temperature is 65°C, and the stretching multiple is 2.80, to obtain the antibacterial modified polyester hollow fiber.

[0042] Example 4

[0043] (1) 0.1 mol of nitrilotriacetic acid is added to xylene, stirred and dissolved, 0.34 mol of thionyl chloride is added, heated to 60°C, refluxed for 3 h, cooled to room temperature, and distilled under reduced pressure to obtain nitrilotriacetyl chloride.

[0044] (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.

[0045] (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.

[0046] (4) 10 g of graphene oxide was added to deionized water, ultrasonically dispersed, 23 g of eugenol epoxy quaternary ammonium salt was added thereto, the temperature was controlled at 65°C, and stirred for 10 h, after the reaction was completed, centrifugation was performed, washed with deionized water, and dried to obtain modified graphene.

[0047] (5) 2 g of dried modified graphene was uniformly mixed with 100 g of polyethylene terephthalate, added to an extruder, plasticized and melted, 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 multiple was 2.80, to obtain an antibacterial modified polyester hollow fiber.

[0048] Example 5

[0049] (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 55°C, refluxed for 4 h, after the reaction was completed, the temperature was lowered to room temperature, and vacuum distillation was performed to obtain nitrilo triacetyl chloride.

[0050] (2) 0.15 mol of nitrilo triacetyl chloride and 0.21 mol of epichlorohydrin were added to methanol, stirred and dispersed, heated to 55°C, reacted for 8 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.

[0051] (3) 0.3 mol of eugenol and 0.32 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 36 h, after the reaction was completed, filtration was performed, and vacuum distillation was performed to obtain an eugenol epoxy quaternary ammonium salt.

[0052] (4) Add 10g of graphene oxide to deionized water, disperse it by ultrasonication, then add 25g of eugenol-based epoxy quaternary ammonium salt, control the temperature at 65℃, stir and react for 10h, after the reaction is completed, centrifuge, wash with deionized water, dry, and obtain modified graphene.

[0053] (5) Mix 2.5g of dried modified graphene with 100g of polyethylene terephthalate evenly, add it to the extruder, plasticize and melt it, and then enter the spinning box and extrude it through the spinneret. After cooling, it is wound and stretched. The spinning temperature is 285℃, the ring blowing speed is 3.4m / s, the ring blowing temperature is 22℃, the stretching temperature is 65℃, and the stretching ratio is 2.80 to obtain antibacterial modified polyester hollow fiber.

[0054] Comparative Example 1

[0055] The preparation method of the polyester hollow fiber provided in this comparative example is roughly the same as that in Example 1. The main difference is that in step (5), graphene is used instead of modified graphene.

[0056] Comparative Example 2

[0057] The preparation method of the polyester hollow fiber provided in this comparative example is roughly the same as that in Example 1. The main difference is that in step (5), eugenol-based epoxy quaternary ammonium salt is used instead of modified graphene.

[0058] The antibacterial properties of polyester hollow fiber were tested according to GB / T20944.3-2008, and the test strains were Staphylococcus aureus and Escherichia coli.

[0059] Table 1:

[0060]

[0061] As shown in the table, the polyester hollow fiber prepared by this invention has good antibacterial properties, with an antibacterial rate of up to 99.9%.

[0062] The mechanical properties of polyester hollow fibers were tested using an electronic single-fiber tensile tester.

[0063] Table 2:

[0064]

[0065] As shown in the table, the polyester hollow fiber prepared by this invention has good breaking strength, with the highest breaking strength reaching 5.08 cN / dtex.

[0066] For anyone skilled in the art, many possible variations and modifications can be made to the technical solutions of this invention, or equivalent embodiments can be modified based on the disclosed technical content, without departing from the scope of the technical solutions of this invention. Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of this invention without departing from the content of the technical solutions of this invention should still fall within the protection scope of the technical solutions of this invention.

Claims

1. A method for preparing an antibacterial modified polyester hollow fiber, characterized in that, The preparation method is as follows: (1) graphene oxide is added to deionized water, ultrasonic dispersion, then eugenol epoxy quaternary ammonium salt is added, the temperature is controlled at 60-70℃, stirring reaction for 8-12h, after the reaction is completed, centrifugation, deionized water washing, drying, to obtain modified graphene; (2) the dried modified graphene is mixed with polyethylene terephthalate uniformly, added to the extruder, plasticized and melted, then extruded through the spinning pack assembly, after cooling, winding, drawing, to obtain antibacterial modified polyester hollow fiber; The preparation method of eugenol epoxy quaternary ammonium salt is as follows: S1, nitrilotriacetic acid is added to xylene, stirring and dissolving, then thionyl chloride is added, heated to 50-60℃, reflux reaction for 2-4h, after the reaction is completed, the temperature is reduced to room temperature, reduced pressure distillation, to obtain nitrilotriacetyl chloride; S2, nitrilotriacetyl chloride and epichlorohydrin are added to methanol, stirring and dispersing, heated to 50-55℃, reaction for 8-12h, after the reaction is completed, the temperature is reduced to room temperature, rotary evaporation, ether washing, drying, to obtain triacetyl chloride epoxy quaternary ammonium salt; S3, eugenol and triethylamine are added to xylene, stirring and dissolving, then triacetyl chloride epoxy quaternary ammonium salt is added, stirring reaction at room temperature for 20-36h, after the reaction is completed, filtration, reduced pressure distillation, to obtain eugenol epoxy quaternary ammonium salt.

2. The method of producing an antibacterial modified polyester hollow fiber according to claim 1, characterized by, In the (1), the amount ratio of graphene oxide and eugenol epoxy quaternary ammonium salt is 100g:(150-250)g.

3. The method of producing an antibacterial modified polyester hollow fiber according to claim 1, characterized by, In the (2), the amount ratio of modified graphene and polyethylene terephthalate is (0.5-2.5)g:100g.

4. The method of producing an antibacterial modified polyester hollow fiber according to claim 1, characterized by, In the (2), the spinning temperature is 285℃; the ring blowing air speed is 3.4m / s, the ring blowing temperature is 22℃; the drawing temperature is 65℃, and the drawing multiple is 2.

80.

5. The method of producing an anti-bacterial modified polyester hollow fiber according to claim 1, characterized in that, In the S1, the amount ratio of nitrilotriacetic acid and thionyl chloride is 1mol:(3-3.5)mol.

6. The method of producing an anti-bacterial modified polyester hollow fiber according to claim 1, characterized in that, In the S2, the amount ratio of nitrilotriacetyl chloride and epichlorohydrin is 1mol:(1-1.4)mol.

7. The method of producing an anti-bacterial modified polyester hollow fiber according to claim 1, characterized in that, 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:1mol.

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