Bio-based nylon 6 fiber with antibacterial function and preparation method thereof

Abstract

According to the bio-based nylon-6 fiber with the antibacterial function and the preparation method of the bio-based nylon-6 fiber, the prepared fiber has high antibacterial performance under the condition that an antibacterial agent is not added, and the problems that antibacterial nylon-6 fibers in the current market are environmentally friendly, efficient in antibacterial performance, durable and the like are solved. The preparation process of the fiber comprises the following steps: (1) putting a certain amount of bio-based nylon 6 raw material in a nitrogen atmosphere, purging and drying for several hours; (2) feeding a bio-based nylon 6 raw material, an auxiliary agent, an antibacterial agent and essential oil into a single-screw extruder from a feeding hole according to a certain proportion; (3) adjusting the rotating speed of the single-screw extruder and the temperature of each area for melting, and then conveying to a spinning die head through a metering pump for extruding to form a plurality of filaments; and (4) bundling the filaments into a single fiber through an oiling wheel, carrying out thermal stretching orientation, and finally winding to form a finished product fiber.

Description

Technical Field

[0001] The invention discloses a method for preparing nylon 6, and particularly relates to a bio-based nylon 6 fiber with antibacterial function and a preparation method thereof, belonging to the field of polymer materials. Background Art

[0002] Polycaprolactam has excellent wear resistance, moisture absorption, resilience, alkali corrosion resistance, mechanical properties, etc. Its comprehensive performance is better than that of polyester, so it is widely used in high-end underwear, stockings, fabrics, safety ropes and other fields. It also has good biocompatibility and has great potential in medical devices, coatings, tissue engineering and other fields. However, its antibacterial, antistatic and heat resistance are poor, and the woven clothes have poor shape retention, which greatly limits the use of polycaprolactam.

[0003] By improving the antibacterial properties of polycaprolactam, its application in the field of health and wellness has always been the focus of attention of foreign academic and industrial circles. However, most of them are prepared by blending polycaprolactam with small molecule additives, such as adding small molecule antibacterial agents such as silver ions and copper ions to prepare polycaprolactam with antibacterial function. This kind of polycaprolactam with antibacterial function has many problems in terms of safety, environmental friendliness, and high efficiency and durability of antibacterial. Therefore, it is very important to directly produce self-cleaning / bactericidal caprolactam polymer base materials by copolymerizing functional monomers and caprolactam.

[0004] With the development of economy, people will pay more attention to their health and safety, and the market demand for sterilization materials to prevent cross infection and hospital infection will be huge. The research and development and application of antibacterial polycaprolactam have received more attention from domestic academic and health industry.

[0005] At present, the domestic antibacterial polycaprolactam is mainly prepared by blending polycaprolactam with small molecule additives. However, this type of polycaprolactam material with antibacterial function still has many problems in terms of safety, environmental friendliness, and high efficiency and durability of antibacterial properties. Summary of the invention

[0006] The purpose of the present invention is to overcome the difficulties of the prior art and provide a bio-based nylon 6 fiber with antibacterial function and a preparation method thereof.

[0007] The main technical scheme of the present invention is: a bio-based nylon 6 fiber with antibacterial function, characterized in that it is made by using bio-based nylon 6 as raw material, adding auxiliary agents, antibacterial agents and essential oils, and through a spinning preparation process; the amount of the bio-based nylon 6 raw material is 90.0-99.9wt%, the amount of the auxiliary agent is 0.04-5.0wt%, the amount of the antibacterial agent is 0.03-5.0wt%, and the amount of the essential oil is 0.03-2.0wt%.

[0008] Preferably, the amount of the bio-based nylon 6 raw material is 98.0-99.5wt%, the amount of the auxiliary agent is 0.3-1.0wt%, the amount of the antibacterial agent is 0.03%-0.5wt%, and the amount of the essential oil is 0.03%-0.5wt%.

[0009] Preferably, the bio-based nylon 6 raw material is nylon 6 prepared by polymerizing biomass materials, and the bio-based nylon 6 raw material is bio-based nylon 6 powder.

[0010] More preferably, the biomass material is lysine. Lysine is used as the starting material, and cyclic lysine monomers with different functional side groups are prepared by ring formation and protection groups, and then the cyclic lysine monomers are copolymerized with caprolactam to obtain bio-based nylon 6 raw materials.

[0011] The method for preparing the bio-based nylon 6 fiber with antibacterial function of the present invention is characterized by comprising the following steps: (1) Pre-treating the bio-based nylon 6 raw material; (2) Putting bio-based nylon 6 raw materials, additives, antimicrobial agents, and essential oils into a single screw extruder; (3) After melting, it is sent to the spinning die through a metering pump; (4) Winding into wire.

[0012] Furthermore, the specific preparation method comprises the following steps: (1) placing a certain amount of bio-based nylon 6 raw material in a nitrogen atmosphere for blowing and drying for several hours; (2) feeding the bio-based nylon 6 raw material, additives, antibacterial agents, and essential oils into the above-mentioned single screw extruder from a feed port in a certain proportion; (3) Adjust the speed of the single screw extruder and the temperature of each zone to melt, and then send it to the spinning die through a metering pump to extrude several filaments; (4) The filaments are bundled into single fibers by an oil wheel, then oriented by heat stretching, and finally wound to form finished fibers.

[0013] More preferably, in step (1), the purge drying is performed for 3 to 48 hours, preferably 5 to 8 hours.

[0014] The auxiliary agent includes a soluble auxiliary agent that needs to be added in the spinning process, wherein the type of antioxidant is at least one of β-(4-hydroxy-3,5-di-tert-butylphenyl) propionate octadecyl, tris(nonylphenol) phosphite, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, bis(2,4-di-tert-butylphenol) pentaerythritol diphosphite, didodecyl thiodipropionate and tris(2,4-di-tert-butylphenyl) phosphite, and preferably β-(4-hydroxy-3,5-di-tert-butylphenyl) propionate octadecyl, tris(nonylphenol) phosphite and tris(2,4-di-tert-butylphenyl) phosphite are compounded.

[0015] The antibacterial agent is at least one of chitosan quaternary ammonium salt, silver ion antibacterial agent and zinc ion antibacterial agent, preferably chitosan quaternary ammonium salt.

[0016] The essential oil is at least one of eucalyptus essential oil, lavender essential oil, tea tree essential oil, cypress essential oil and thyme essential oil, preferably a composite of eucalyptus essential oil, cypress essential oil and thyme essential oil.

[0017] The single screw extruder has a rotation speed of 30 to 60 rpm, preferably 40 to 50 rpm.

[0018] The temperature of each zone of the single screw extruder refers to that zone 1 is a single screw feeding zone with a temperature of 240-280°C, preferably 260-270°C; zone 2 is a single screw melting zone with a temperature of 240-280°C, preferably 255-275°C; zone 3 is a single screw melting zone with a temperature of 240-280°C, preferably 265-280°C; zone 4 is a single screw outlet zone with a temperature of 240-280°C, preferably 265-280°C.

[0019] The beneficial effects of the present invention are as follows: the method of the present invention can produce a new type of bactericidal caprolactam polymer fiber material which is environmentally friendly and has long-lasting and efficient antibacterial properties, thereby further improving the antibacterial properties of medical protective materials, which has very important social significance and significant economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The figure is a schematic diagram of the process of preparing bio-based nylon 6 fiber with antibacterial function in an embodiment of the present invention. Implementation

[0021] In order to make the technical problems to be solved, technical solutions and advantages of the present invention more clear, a detailed description will be given below in conjunction with specific embodiments and drawings.

[0022] The preparation method of the bio-based nylon 6 fiber with antibacterial function in the following embodiments is shown in the attached Figure 1, mainly including the following steps: placing a certain amount of bio-based nylon 6 raw material in a nitrogen atmosphere for several hours; feeding the bio-based nylon 6 raw material, additives, antibacterial agents, and essential oils into the above-mentioned single screw extruder from the feed port in a certain proportion; adjusting the speed of the single screw extruder and the temperature of each zone for melting, and then sending it to the spinning die head through a metering pump for extrusion to form several filaments; the filaments are bundled into single fibers through an oiling wheel, and then oriented by thermal stretching, and finally wound to form finished fibers. The amount of bio-based nylon 6 raw material is 98.0-99.5wt%, the amount of the additive is 0.3-1.0wt%, the amount of the antibacterial agent is 0.03%-0.5wt%, and the amount of the essential oil is 0.03%-0.5wt%.

[0023] Bio-based nylon 6 fiber antibacterial test: absorption method. This test method refers to the absorption method in the international standard ISO 20743-2005 "Textiles-Determination of the activity of antibacterial finishing products", which is a quantitative test of the antibacterial properties of textiles. During the test, the sample and the control sample are inoculated with the test bacterial solution, and the elution is performed immediately and after incubation. The number of bacteria in the elution solution is determined and the antibacterial value or antibacterial rate is calculated to evaluate the antibacterial effect of the sample.

[0024] The following describes the invention in conjunction with embodiments. Example

[0025] (1) A certain amount of bio-based nylon 6 raw material was placed in a nitrogen atmosphere for purging and drying for 5 hours; (2) A certain amount of bio-based nylon 6 raw material, 0.4wt% antioxidant (compounded with β-(4-hydroxy-3,5-di-tert-butylphenyl) propionate octadecyl, tris(nonylphenol) phosphite, and tris(2,4-di-tert-butylphenyl) phosphite), 0.05wt% chitosan quaternary ammonium salt, and 0.05wt% essential oil (compounded with eucalyptus essential oil, cypress essential oil, and thyme essential oil) were fed into a single screw extruder from a feed port in a certain proportion; (3) adjusting the speed of the single-screw extruder to 45 rpm, and setting the temperature of zone 1 of the twin-screw extruder to 260-270°C; the temperature of zone 2 to 255-275°C; the temperature of zone 3 to 265-280°C; and the temperature of zone 4 to 265-280°C for melting, and then delivering the mixture to the spinning die through a metering pump for extrusion to form several filaments; (4) The filaments are bundled into single fibers by an oil wheel, then oriented by heat stretching, and finally wound to form finished fibers.

[0026] (5) The finished fiber is subjected to antibacterial test.

[0027] According to the fiber production steps and antibacterial test, 8 groups of examples and 3 groups of comparative examples were carried out (Comparative Example 1 used commercially available bio-based nylon 6 raw materials instead of the bio-based nylon 6 polymerized by lysine as described in this patent, Comparative Example 2 did not add antibacterial agent, and Comparative Example 3 did not add essential oil). The difference between the groups of examples lies in the different addition amounts of bio-based nylon 6 raw materials (the part less than 99.5% was supplemented to 99.5% using commercially available bio-based nylon 6 raw materials). The antibacterial test results of each group are shown in Table 1.

[0028] Table 1 Antibacterial test data .

[0029] It can be seen from the experimental data results of the embodiments and comparative examples that the fiber prepared using the bio-based nylon 6 raw material of the present invention has very excellent antibacterial properties.

Claims

1. A bio-based nylon 6 fiber with antibacterial function, characterized in that: The bio-based nylon 6 is used as a raw material, and auxiliary agents, antibacterial agents and essential oils are added to obtain the product through a spinning preparation process; the amount of the bio-based nylon 6 raw material is 90.0-99.9wt%, the amount of the auxiliary agent is 0.04-5.0wt%, the amount of the antibacterial agent is 0.03-5.0wt%, and the amount of the essential oil is 0.03-2.0wt%.

2. The bio-based nylon 6 fiber with antibacterial function according to claim 1, characterized in that The amount of the bio-based nylon 6 raw material is 98.0-99.5wt%, the amount of the auxiliary agent is 0.3-1.0wt%, the amount of the antibacterial agent is 0.03%-0.5wt%, and the amount of the essential oil is 0.03%-0.5wt%.

3. The bio-based nylon 6 fiber with antibacterial function according to claim 1 or 2, characterized in that The bio-based nylon 6 raw material is nylon 6 prepared by polymerizing biomass materials, and the bio-based nylon 6 raw material is bio-based nylon 6 powder.

4. The bio-based nylon 6 fiber with antibacterial function according to any one of claims 1 to 3, characterized in that The biomass material is lysine.

5. The method for preparing the bio-based nylon 6 fiber with antibacterial function according to claim 1, characterized in that The following steps are involved: (1) Pre-treating the bio-based nylon 6 raw material; (2) Putting bio-based nylon 6 raw materials, additives, antibacterial agents, and essential oils into a single screw extruder; (3) After melting, it is sent to the spinning die through a metering pump; (4) Winding into wire.

6. The preparation method according to claim 5, characterized in that The following steps are involved: (1) Place the bio-based nylon 6 raw material in a nitrogen atmosphere for several hours; (2) feeding the bio-based nylon 6 raw material, additives, antibacterial agents, and essential oils into a single screw extruder from a feed port in proportion; (3) Adjust the speed of the single screw extruder and the temperature of each zone to melt, and then send it to the spinning die through a metering pump to extrude several filaments; (4) The filaments are bundled into single fibers by an oil wheel, then oriented by heat stretching, and finally wound to form finished fibers.

7. The preparation method according to claim 6, characterized in that In step (1), the purge drying is performed for 3 to 48 hours, preferably 5 to 8 hours.

8. The preparation method according to claim 6, characterized in that The auxiliary agent includes a soluble auxiliary agent that needs to be added in the spinning process, wherein the type of antioxidant is at least one of β-(4-hydroxy-3,5-di-tert-butylphenyl) propionate octadecyl, tris(nonylphenol) phosphite, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, bis(2,4-di-tert-butylphenol) pentaerythritol diphosphite, didodecyl thiodipropionate and tris(2,4-di-tert-butylphenyl) phosphite, and preferably β-(4-hydroxy-3,5-di-tert-butylphenyl) propionate octadecyl, tris(nonylphenol) phosphite and tris(2,4-di-tert-butylphenyl) phosphite are compounded.

9. The preparation method according to claim 6, characterized in that The antibacterial agent is at least one of chitosan quaternary ammonium salt, silver ion antibacterial agent and zinc ion antibacterial agent, preferably chitosan quaternary ammonium salt.

10. The preparation method according to claim 6, characterized in that The essential oil is at least one of eucalyptus essential oil, lavender essential oil, tea tree essential oil, cypress essential oil and thyme essential oil, preferably a composite of eucalyptus essential oil, cypress essential oil and thyme essential oil.

11. The preparation method according to claim 6, characterized in that The single screw extruder has a rotation speed of 30 to 60 rpm, preferably 40 to 50 rpm.

12. The preparation method according to claim 6, characterized in that The temperature of each zone of the single screw extruder refers to that zone 1 is a single screw feeding zone with a temperature of 240-280°C, preferably 260-270°C; zone 2 is a single screw melting zone with a temperature of 240-280°C, preferably 255-275°C; zone 3 is a single screw melting zone with a temperature of 240-280°C, preferably 265-280°C; zone 4 is a single screw outlet zone with a temperature of 240-280°C, preferably 265-280°C.

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