Method for preparing conductive nylon 6 fiber by using modified conductive carbon black

Abstract

The invention discloses a method for preparing conductive nylon 6 fiber by using modified conductive carbon black, and belongs to the technical field of fine chemical engineering. According to the invention, polyvinylpyrrolidone, modified polyacrylic acid and styrene-maleic anhydride copolymer hyperdispersant aqueous solutions are added in the cooling link of conductive carbon black production, so that the physical and chemical properties of the surface of the conductive carbon black can be changed, and the compatibility of the modified conductive carbon black and a nylon system is enhanced; therefore, the conductive effect of the conductive carbon black in nylon is improved, and the problems of poor dispersion performance, poor spinnability, too high filter pressing value and the like of the conductive carbon black in nylon fiber melt spinning are solved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of fine chemical industry, and particularly relates to a method for preparing conductive nylon 6 fiber by using modified conductive carbon black. BACKGROUND

[0002] Static electricity is everywhere in life and brings many inconveniences to people's production and life. For example, static electricity caused by dry weather in winter leads to fire, and static electricity caused by friction of clothes fabric leads to human body contact discomfort. The traditional anti-static method mainly coats an antistatic agent on the surface of plastic or fiber fabric, or prepares a conductive master batch and then applies it to plastic or fiber. However, the traditional coating method is easy to fall off during the use of plastic or fabric, resulting in reduced or lost anti-static effect. Therefore, the conductive master batch is applied to the fabric, and the anti-static effect is more durable and the cost is lower. Common conductive fillers are mostly graphene, carbon nanotubes, conductive carbon black, metal powder, etc., which can provide good anti-static effect for the fabric and realize coloring. Among them, conductive carbon black has relatively high cost performance as a conductive filler and is widely used in plastic products or fabrics.

[0003] Conductive carbon black is a new type of conductive material derived from the conductive performance of carbon black material, which has excellent conductive performance and low price, and is commonly used in electronic product shells, plastic cables, conductive fibers and other fields. The current conductive carbon black generally needs to be obtained under high temperature conditions, mainly by oil furnace method with air combustion. This process has high energy consumption, and the produced conductive carbon black has many impurities. Therefore, the conductive carbon black produced by the traditional process is easy to agglomerate in the fiber, has poor dispersion performance, and thus reduces the anti-static effect. Therefore, how to improve the compatibility and dispersion of conductive carbon black in the fiber matrix and thus improve its anti-static performance in the fiber is a problem to be solved at present.

[0004] Nylon 6 fiber has excellent mechanical strength, wear resistance, corrosion resistance and other properties, and is one of the synthetic chemical fibers with the largest use in current life. Conductive nylon 6 fiber is also one of the current research focuses, so improving the dispersion performance of conductive carbon black in nylon 6 fiber is of great significance for the development of high-performance nylon 6 fiber. SUMMARY

[0005] [TECHNICAL PROBLEM]

[0006] The technical problem to be solved by the present application is that the existing conductive carbon black is easy to agglomerate in the fiber, has poor dispersion performance, and reduces the anti-static effect of the fiber.

[0007] [TECHNICAL SCHEME]

[0008] In order to solve the above problems, the application provides a method for preparing conductive nylon 6 fibers by using modified conductive carbon black. The method can change the physical and chemical properties of the surface of the conductive carbon black by adding an aqueous solution of a hyperdispersant in the cooling process of the production of the conductive carbon black, thereby enhancing the compatibility of the modified conductive carbon black with the nylon system and improving the conductive effect of the conductive carbon black in the nylon. The method can solve the problems of poor dispersing performance, poor spinnability and high pressure filtration value of the conductive carbon black in the melt spinning of the nylon fibers.

[0009] The application provides a method for preparing conductive nylon 6 fibers by using modified conductive carbon black, which comprises the following steps:

[0010] (1) Firstly, the coal tar is preheated to 130-150 DEG C, and then a high-temperature composite gas stream is sent into a reaction furnace, wherein the high-temperature composite gas stream and the coal tar are used as reaction raw materials; the high-temperature composite gas stream comprises a plasma jet, a natural gas cyclone and an air cyclone, and the temperature is 2000-4000 DEG C, wherein the volume ratio of the plasma jet, the natural gas cyclone and the air cyclone is 10-20: 15-30: 50-75;

[0011] (2) The oil gas (coal tar, air, natural gas and plasma jet mixed gas) mixed in the throat pipe is introduced into a cracking zone, the average temperature is 1800-2500 DEG C, and the reaction residence time is not less than 500 ms, so that the conductive carbon black and flue gas are rapidly cracked;

[0012] (3) The cooling water is introduced into the reaction furnace to rapidly reduce the temperature and terminate the reaction;

[0013] (4) When the temperature of the reaction furnace is reduced to 200-300 DEG C, the aqueous solution mixed with the hyperdispersant is introduced into the reaction furnace to rapidly reduce the temperature and make the hyperdispersant wrapped on the surface of the carbon black;

[0014] (5) The conductive carbon black and the flue gas after cooling are separated and collected by a bag filter, and are granulated by a dry granulation method, so as to prepare the conductive carbon black granules;

[0015] (6) The prepared conductive carbon black is dried in a 100 DEG C vacuum oven for 4-6 h, and the PA6 resin powder is dried in a 100 DEG C vacuum oven for 4-6 h;

[0016] (7) Then, the dried PA6 powder, the conductive carbon black and the processing aid are uniformly blended according to a certain proportion, and are sequentially subjected to a melt extrusion process by a double-screw extruder and a water-cooling granulation process, so as to prepare a PA conductive master batch.

[0017] (8) Put the PA conductive master batch into a vacuum oven at 80-100℃, dry for 8-12h, reduce the moisture content to below 50ppm, mix evenly with PA6 fiber grade spinning chip according to the ratio of 1:4, melt spinning to prepare conductive nylon 6 fiber.

[0018] In one embodiment of the present application, in step (1), the plasma jet is formed by an electric arc generated by a plasma torch with a circulating tail gas; the circulating tail gas flow is 400 Nm 3 / h, the natural gas flow is 600 Nm 3 / h, the air flow is 2400 Nm 3 / h, the plasma operating current is 500 A, and the operating power is 800 kW.

[0019] In one embodiment of the present application, in step (4), the type of the hyperdispersant is one or more of polyvinylpyrrolidone, modified polyacrylic acid, and styrene-maleic anhydride copolymer.

[0020] In one embodiment of the present application, in step (4), the structure of the polyvinylpyrrolidone hyperdispersant is:

[0021]

[0022] Further, w is an integer from 50 to 12000, and the Mn of the polyvinylpyrrolidone hyperdispersant is 8000-1300000.

[0023] In one embodiment of the present application, in step (4), the structure of the modified polyacrylic acid hyperdispersant is:

[0024]

[0025] Further, z is an integer from 10 to 60, R4 is one or more of sodium salt, ammonium salt, and potassium salt; and the Mn of the modified polyacrylic acid hyperdispersant is 1000-5000.

[0026] In one embodiment of the present application, in step (4), the structure of the styrene-maleic anhydride copolymer hyperdispersant is:

[0027]

[0028] wherein m:n is 1:0.03-1:0.15, 10≤m≤200, 0≤n≤40, m and n are both integers; R1 is one of OH, alkyl hydroxyl, and polyester hydroxyl group; R2 is one of OH, alkyl hydroxyl, and polyester hydroxyl group; and the Mn of the styrene-maleic anhydride copolymer hyperdispersant is 10000-40000.

[0029] In one embodiment of the present application, in step (4), the mass fraction of the aqueous solution of the hyperdispersant is 5-25%.

[0030] In one embodiment of the present application, in step (4), the reaction furnace temperature is reduced to 200-270℃, and the aqueous solution of the hyperdispersant is introduced.

[0031] In one embodiment of the present application, in step (6), the moisture content of the conductive carbon black and the PA6 resin powder is controlled to be below 1000 ppm.

[0032] In one embodiment of the present application, in step (7), the mass fraction of the conductive carbon black in the PA conductive masterbatch is 25-35%, the mass fraction of the PA6 powder is 65-75%, and the mass fraction of the processing aid is 1-3%.

[0033] In one embodiment of the present application, in step (7), the processing aid is an antioxidant, and the antioxidant is tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester or a phosphite antioxidant.

[0034] The present application provides a conductive nylon 6 fiber prepared by the above-mentioned method.

[0035] The present application has the following beneficial effects:

[0036] The present application uses a hyperdispersant to modify the surface of the conductive carbon black; the dispersant is added during the production of the conductive carbon black, which helps the conductive carbon black to be more uniformly dispersed in the nylon 6 fiber. The hyperdispersant is wrapped on the surface of the conductive carbon black, and a conductive masterbatch is prepared and applied to the melt spinning of the nylon 6 fiber, which can avoid the agglomeration of the conductive carbon black particles in the nylon fiber, solve the problems of high pressure filtration value, poor spinnability, and poor conductivity during the spinning of the conductive nylon, and improve the antistatic performance of the conductive nylon fiber. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 Figure 2 is a SEM image of a conductive nylon 6 fiber, wherein (a) is a nylon 6 fiber without the addition of conductive carbon black; (b) is a conductive nylon 6 fiber prepared in Example 4; (c) is a conductive nylon 6 fiber prepared in Example 10; (d) is a conductive nylon 6 fiber prepared in Example 11; (e) is a conductive nylon 6 fiber prepared by using domestic conductive carbon black in Comparative Example 3; and (f) is a conductive nylon 6 fiber prepared by using imported conductive carbon black in Comparative Example 4. DETAILED DESCRIPTION

[0038] The preferred embodiments of the present application are described below, and it should be understood that the embodiments are used to better explain the present application and are not used to limit the present application.

[0039] In the following examples, the carrier resin is polyamide 6 resin, which is a common commercialized resin in the color masterbatch industry.

[0040] Performance test methods used in the present application:

[0041] Carbon black heat resistance test: The thermal decomposition performance of the sample was analyzed by thermogravimetric analysis (TG), under a nitrogen atmosphere, at a heating rate of 10℃ / min, from 25℃ to 800℃.

[0042] Filtering performance test: Add 500g of PA6 chips to the washing equipment to make the melt pressure curve run smoothly, and record the initial pressure P0; then add 500g of a mixture of color masterbatch and PA6 chips, with a mass ratio of 1:1, and after the material is used up, add 500g of PA6 chips, and record the maximum pressure Pmax after 120s. The pigment content in the color masterbatch is m (g), and the filter pressure value FPV = (P max -P0) / m. The experiment uses a 10μm filter screen. The spinnability of the color masterbatch is characterized by the filtering performance test.

[0043] Fiber surface morphology observation: The prepared conductive nylon fibers were placed on aluminum foil and treated with gold spraying at an acceleration voltage of 30kV, and the cross-sectional morphology of the samples was observed using a scanning electron microscope (SU1510, USA). Compared with nylon fiber filaments without carbon black under the same process, √ indicates that the cross-sectional morphology is basically similar to that of the conductive nylon fiber filaments, Δ indicates a few particles, and ╳ indicates obvious particles.

[0044] According to the national standard GB / T14344-2008 "Chemical fiber filament tensile property test method", the breaking strength of nylon 6 fiber filaments and conductive nylon fibers was tested, and the test conditions were: clamping length 20mm, tensile speed 20mm / min.

[0045] Resistivity test: The two-electrode method was used to test the resistivity of the conductive fiber, and the current was injected into the conductive fiber through two electrodes, while the voltage was measured, so as to calculate the resistivity of the conductive fiber.

[0046] In the following examples, the plasma jet is formed by circulating tail gas passing through the plasma torch to generate an arc; the circulating tail gas flow is 400Nm 3 / h, the natural gas flow is 600Nm 3 / h, the air flow is 2400Nm 3 / h, the plasma operating current is 500A, and the operating power is 800kW; refer to patent CN119264704 A.

[0047] In the following examples, the antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], which is BASF antioxidant 1010.

[0048] Example 1

[0049] (1) First, the coal tar is preheated and a high-temperature compound gas stream is prepared, the raw oil is preheated to 140°C, and then the high-temperature compound gas stream is subsequently fed into the reaction furnace, and the high-temperature compound gas stream and the coal tar are used as the reaction raw materials.

[0050] (2) The high-temperature compound gas stream includes a plasma jet, a natural gas vortex, and an air vortex. The temperature is about 3000°C, and the volume ratio of the plasma jet:natural gas vortex:air vortex is 20:15:65.

[0051] (3) The oil gas mixed in the throat pipe is introduced into the cracking zone, the average temperature is 1800-2500°C, the reaction residence time is 600 ms, and the conductive carbon black and flue gas are rapidly cracked.

[0052] (4) Cooling water is fed into the reaction furnace to rapidly reduce the temperature and terminate the reaction.

[0053] (5) When the reaction furnace temperature drops to 250°C, an aqueous solution of polyvinylpyrrolidone mixed with the coal tar is fed into the reaction furnace at a mass ratio of 0.33:1, so that the temperature is rapidly reduced, and the dispersant is wrapped on the surface of the carbon black. The cooled carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used for granulation, and then carbon black particles are prepared, wherein the Mn of the polyvinylpyrrolidone is about 8000 (Guo Yao reagent K16), and the concentration is 15wt%; the dispersant structure is as follows:

[0054]

[0055] (6) The cooled conductive carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used for granulation, and then conductive carbon black particles are prepared.

[0056] (7) The prepared conductive carbon black is placed in a 100°C vacuum oven for drying treatment for 6h, and the PA6 resin powder is placed in a 100°C vacuum oven for drying treatment for 5h.

[0057] (8) Then, the dried PA6 powder, conductive carbon black, and antioxidant are uniformly blended at a ratio of 69:30:1, and sequentially subjected to melt extrusion by a twin-screw extruder, water cooling granulation, and other processes to prepare a PA conductive masterbatch.

[0058] (9) Put the color master batch into a vacuum oven at 80℃, dry for 8-12h, and reduce the moisture content to below 50ppm. Then mix the PA6 fiber grade spinning chip in a ratio of 1:4, melt-spinning to obtain conductive nylon 6 fiber.

[0059] Example 2

[0060] (1) First, preheat the coal tar and prepare the high-temperature compound gas stream. Preheat the raw oil to 140℃, and then send the high-temperature compound gas stream into the reaction furnace. The high-temperature compound gas stream and the coal tar are used as reaction raw materials.

[0061] (2) The high-temperature compound gas stream includes plasma jet, natural gas vortex, and air vortex. The temperature is about 3000℃, and the volume ratio of plasma jet:natural gas vortex:air vortex is 20:15:65.

[0062] (3) The oil and gas mixture in the throat pipe is introduced into the cracking zone, and the average temperature is 2000℃. The reaction residence time is 600ms, and the conductive carbon black and flue gas are rapidly cracked.

[0063] (4) The reaction furnace is cooled by passing cooling water into the reaction furnace to rapidly reduce the temperature and terminate the reaction.

[0064] (5) When the temperature of the reaction furnace is reduced to 250℃, an aqueous solution of polyvinylpyrrolidone mixed with the coal tar is introduced into the reaction furnace in a ratio of 0.33:1 by mass, so that the temperature is rapidly reduced, and the dispersant is wrapped on the surface of the carbon black. The cooled carbon black and flue gas are separated and collected by a bag filter, and are granulated by a dry granulation method to obtain carbon black particles. The Mn of the polyvinylpyrrolidone is about 10000 (Guojia Reagent K18), and the concentration is 15wt%; the structure of the dispersant is as follows:

[0065]

[0066] (6) The cooled conductive carbon black and flue gas are separated and collected by a bag filter, and are granulated by a dry granulation method to obtain conductive carbon black particles.

[0067] (7) The prepared conductive carbon black is placed in a vacuum oven at 100℃ for drying treatment for 6h, and the PA6 resin powder is placed in a vacuum oven at 100℃ for drying treatment for 5h.

[0068] (8) Then, the dried PA6 powder, conductive carbon black, and antioxidant are uniformly blended in a ratio of 69:30:1, and are sequentially subjected to melt extrusion by a twin-screw extruder, water-cooled granulation, and other processes to obtain a PA conductive master batch.

[0069] (9) Put the color master batch into a vacuum oven at 80℃, dry for 8-12h, and reduce the moisture content to below 50ppm. Then mix the PA6 fiber grade spinning chip in a ratio of 1:4, melt-spinning to obtain conductive nylon 6 fiber.

[0070] Example 3

[0071] (1) First, preheat the coal tar and prepare the high-temperature compound gas stream. Preheat the raw oil to 140℃, and then send the high-temperature compound gas stream into the reaction furnace. The high-temperature compound gas stream and the coal tar are used as reaction raw materials.

[0072] (2) The high-temperature compound gas stream includes plasma jet, natural gas vortex, and air vortex. The temperature is about 3000℃, and the volume ratio of plasma jet:natural gas vortex:air vortex is 20:15:65.

[0073] (3) The oil and gas mixture in the throat pipe is introduced into the cracking zone at an average temperature of 2000℃. The reaction residence time is 600ms, and the conductive carbon black and flue gas are rapidly cracked.

[0074] (4) Cool down the reaction furnace by introducing cooling water to rapidly reduce the temperature and terminate the reaction.

[0075] (5) When the reaction furnace temperature drops to 250℃, introduce the polyvinylpyrrolidone aqueous solution into the reaction furnace at a mass ratio of 0.33:1 to the coal tar, rapidly reduce the temperature, and wrap the carbon black surface with the dispersant. The cooled carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used for granulation to obtain carbon black particles. The polyvinylpyrrolidone has Mn≈40000 (Guojia Reagent K25) and a concentration of 15wt%; the dispersant has the following structure:

[0076]

[0077] (6) The cooled conductive carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used for granulation to obtain conductive carbon black particles.

[0078] (7) The prepared conductive carbon black is placed in a 100℃ vacuum oven for drying treatment for 6h, and the PA6 resin powder is placed in a 100℃ vacuum oven for drying treatment for 5h.

[0079] (8) Then, the dried PA6 powder, conductive carbon black, and antioxidant are uniformly blended in a ratio of 69:30:1, and sequentially subjected to melt extrusion by a twin-screw extruder, water-cooled granulation, and other processes to obtain a PA conductive master batch.

[0080] (9) Put the color master batch into a vacuum oven at 80℃, dry for 8-12h, and reduce the moisture content to below 50ppm. Then mix the PA6 fiber grade spinning chip in a ratio of 1:4, melt-spinning to obtain conductive nylon 6 fiber.

[0081] Example 4

[0082] (1) First, preheat the coal tar and prepare the high-temperature compound gas stream. Preheat the raw oil to 140℃, and then send the high-temperature compound gas stream into the reaction furnace. The high-temperature compound gas stream and the coal tar are used as reaction raw materials.

[0083] (2) The high-temperature compound gas stream includes plasma jet, natural gas vortex, and air vortex. The temperature is about 3000℃, and the volume ratio of plasma jet:natural gas vortex:air vortex is 20:15:65.

[0084] (3) The oil and gas mixture in the throat pipe is introduced into the cracking zone, and the average temperature is 2000℃. The reaction residence time is 600ms, and the conductive carbon black and flue gas are rapidly cracked.

[0085] (4) The reaction furnace is supplied with cooling water to rapidly reduce the temperature and terminate the reaction.

[0086] (5) When the reaction furnace temperature drops to 250℃, a water solution mixed with polyvinylpyrrolidone is supplied into the reaction furnace at a mass ratio of 0.33:1 with the coal tar, so that the temperature is rapidly reduced, and the dispersant is wrapped on the surface of the carbon black. The cooled carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used for granulation, and then carbon black particles are prepared. The Mn of polyvinylpyrrolidone is about 45000 (Guojia Reagent K30), and the concentration is 15wt%; the dispersant structure is as follows:

[0087]

[0088] (6) The cooled conductive carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used for granulation, and then conductive carbon black particles are prepared.

[0089] (7) The prepared conductive carbon black is placed in a vacuum oven at 100℃ for drying treatment for 6h, and the PA6 resin powder is placed in a vacuum oven at 100℃ for drying treatment for 5h.

[0090] (8) Then, the dried PA6 powder, conductive carbon black, and antioxidant are uniformly blended in a ratio of 69:30:1, and sequentially subjected to melt extrusion by a double-screw extruder, water-cooled granulation, and other processes to obtain a PA conductive master batch.

[0091] (9) Put the color master batch into a vacuum oven at 80℃, dry for 8-12h, and reduce the moisture content to below 50ppm. Then mix the PA6 fiber grade spinning chip in a ratio of 1:4, melt-spinning to obtain conductive nylon 6 fiber.

[0092] Example 5

[0093] (1) First, preheat the coal tar and prepare the high-temperature compound gas stream. Preheat the raw oil to 140℃, and then send the high-temperature compound gas stream into the reaction furnace. The high-temperature compound gas stream and the coal tar are used as reaction raw materials.

[0094] (2) The high-temperature compound gas stream includes plasma jet, natural gas vortex, and air vortex. The temperature is about 3000℃, and the volume ratio of plasma jet:natural gas vortex:air vortex is 20:15:65.

[0095] (3) The oil and gas mixture in the throat pipe is introduced into the cracking zone, and the average temperature is 2000℃. The reaction residence time is 600ms, and the conductive carbon black and flue gas are rapidly cracked.

[0096] (4) The reaction furnace is cooled by passing cooling water to rapidly reduce the temperature and terminate the reaction.

[0097] (5) When the reaction furnace temperature drops to 250℃, a polyvinylpyrrolidone aqueous solution is introduced into the reaction furnace in a ratio of 0.33:1 with the coal tar to rapidly reduce the temperature and wrap the carbon black surface with the dispersant. The cooled carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used to produce carbon black particles. The polyvinylpyrrolidone has a Mn of about 300000 (Guo Yao Reagent K60) and a concentration of 15wt%; the dispersant has the following structure:

[0098]

[0099] (6) The cooled conductive carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used to produce conductive carbon black particles.

[0100] (7) The prepared conductive carbon black is placed in a 100℃ vacuum oven for drying treatment for 6h, and the PA6 resin powder is placed in a 100℃ vacuum oven for drying treatment for 5h.

[0101] (8) Then, the dried PA6 powder, conductive carbon black, and antioxidant are uniformly blended in a ratio of 69:30:1, and sequentially subjected to melt extrusion by a twin-screw extruder, water-cooled granulation, and other processes to produce a PA conductive master batch.

[0102] (9) Put the color master batch into a vacuum oven at 80℃, dry for 8-12h, and reduce the moisture content to below 50ppm. Then mix the PA6 fiber grade spinning chip in a ratio of 1:4, melt-spinning to obtain conductive nylon 6 fiber.

[0103] Example 6

[0104] (1) First, preheat the coal tar and prepare the high-temperature compound gas stream. Preheat the raw oil to 140℃, and then send the high-temperature compound gas stream into the reaction furnace. The high-temperature compound gas stream and the coal tar are used as reaction raw materials.

[0105] (2) The high-temperature compound gas stream includes plasma jet, natural gas vortex, and air vortex. The temperature is about 3000℃, and the volume ratio of plasma jet:natural gas vortex:air vortex is 20:15:65.

[0106] (3) The oil and gas mixture in the throat pipe is introduced into the cracking zone at an average temperature of 2000℃. The reaction residence time is 600ms, and the conductive carbon black and flue gas are rapidly cracked.

[0107] (4) The reaction furnace is supplied with cooling water to rapidly reduce the temperature and terminate the reaction.

[0108] (5) When the reaction furnace temperature drops to 250℃, a water solution mixed with polyvinylpyrrolidone is supplied into the reaction furnace at a mass ratio of 0.33:1 with the coal tar, so that the temperature is rapidly reduced, and the dispersant is wrapped on the surface of the carbon black. The cooled carbon black and flue gas are separated and collected by a bag filter, and are granulated by a dry granulation method to obtain carbon black particles. The polyvinylpyrrolidone has a Mn of about 1300000 (Guojia Reagent K90) and a concentration of 15wt%; the dispersant has the following structure:

[0109]

[0110] (6) The cooled conductive carbon black and flue gas are separated and collected by a bag filter, and are granulated by a dry granulation method to obtain conductive carbon black particles.

[0111] (7) The prepared conductive carbon black is placed in a vacuum oven at 100℃ for drying treatment for 6h, and the PA6 resin powder is placed in a vacuum oven at 100℃ for drying treatment for 5h.

[0112] (8) Then, the dried PA6 powder, conductive carbon black, and antioxidant are uniformly blended in a ratio of 69:30:1, and are sequentially subjected to melt extrusion by a twin-screw extruder, water cooling granulation, and other processes to obtain a PA conductive master batch.

[0113] (9) Put the color master batch into a vacuum oven at 80℃, dry for 8-12h, and reduce the moisture content to below 50ppm. Then mix the PA6 fiber grade spinning chip in a ratio of 1:4, melt-spinning to obtain conductive nylon 6 fiber.

[0114] Example 7

[0115] (1) First, preheat the coal tar and prepare the high-temperature compound gas stream. Preheat the raw oil to 140℃, and then send the high-temperature compound gas stream into the reaction furnace. The high-temperature compound gas stream and the coal tar are used as reaction raw materials.

[0116] (2) The high-temperature compound gas stream includes plasma jet, natural gas vortex, and air vortex. The temperature is about 3000℃, and the volume ratio of plasma jet:natural gas vortex:air vortex is 20:15:65.

[0117] (3) The oil and gas mixture in the throat pipe is introduced into the cracking zone, and the average temperature is 2000℃. The reaction residence time is 600ms, and the conductive carbon black and flue gas are rapidly cracked.

[0118] (4) The reaction furnace is supplied with cooling water to rapidly reduce the temperature and terminate the reaction.

[0119] (5) When the reaction furnace temperature drops to 250℃, a water solution mixed with polyvinylpyrrolidone is supplied into the reaction furnace at a mass ratio of 0.33:1 with the coal tar, so that the temperature is rapidly reduced, and the dispersant is wrapped on the surface of the carbon black. The cooled carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used for granulation, and then carbon black particles are prepared. The Mn of polyvinylpyrrolidone is about 45000 (Guojia Reagent K60), and the concentration is 5wt%; the dispersant structure is as follows:

[0120]

[0121] (6) The cooled conductive carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used for granulation, and then conductive carbon black particles are prepared.

[0122] (7) The prepared conductive carbon black is placed in a 100℃ vacuum oven for drying treatment for 6h, and the PA6 resin powder is placed in a 100℃ vacuum oven for drying treatment for 5h.

[0123] (8) Then, the dried PA6 powder, conductive carbon black, and antioxidant are uniformly blended in a ratio of 69:30:1, and sequentially subjected to melt extrusion by a twin-screw extruder, water cooling granulation, and other processes to prepare a PA conductive master batch.

[0124] (9) Put the color master batch into a vacuum oven at 80℃, dry for 8-12h, and reduce the moisture content to below 50ppm. Then mix the PA6 fiber grade spinning chip in a ratio of 1:4, melt-spinning to obtain conductive nylon 6 fiber.

[0125] Example 8

[0126] (1) First, preheat the coal tar and prepare the high-temperature composite gas flow. Preheat the raw oil to 140℃, and then send the high-temperature composite gas flow into the reaction furnace. The high-temperature composite gas flow and the coal tar are used as reaction raw materials.

[0127] (2) The high-temperature composite gas flow includes plasma jet, natural gas vortex, and air vortex. The temperature is about 3000℃, and the volume ratio of plasma jet:natural gas vortex:air vortex is 20:15:65.

[0128] (3) The oil and gas mixture in the throat pipe is introduced into the cracking zone at an average temperature of 2000℃. The reaction residence time is 600ms, and the conductive carbon black and flue gas are rapidly cracked.

[0129] (4) Cool water is introduced into the reaction furnace to rapidly reduce the temperature and terminate the reaction.

[0130] (5) When the reaction furnace temperature drops to 250℃, an aqueous solution of polyvinylpyrrolidone mixed with the coal tar is introduced into the reaction furnace at a mass ratio of 0.33:1, which rapidly reduces the temperature and allows the dispersant to wrap around the carbon black surface. The cooled carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used to produce carbon black particles. The polyvinylpyrrolidone has a Mn of about 45000 (Guojia Reagent K60) and a concentration of 25wt%; the dispersant has the following structure:

[0131]

[0132] (6) The cooled conductive carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used to produce conductive carbon black particles.

[0133] (7) The prepared conductive carbon black is placed in a 100℃ vacuum oven for drying treatment for 6h, and the PA6 resin powder is placed in a 100℃ vacuum oven for drying treatment for 5h.

[0134] (8) Then, the dried PA6 powder, conductive carbon black, and antioxidant are uniformly blended in a ratio of 69:30:1, and sequentially subjected to melt extrusion by a twin-screw extruder, water-cooled granulation, and other processes to produce a PA conductive master batch.

[0135] (9) Put the color master batch into a vacuum oven at 80℃, dry for 8-12h, and reduce the moisture content to below 50ppm. Then mix the PA6 fiber grade spinning chip in a ratio of 1:4, melt-spinning to prepare conductive nylon 6 fiber.

[0136] Example 9

[0137] (1) First, preheat the coal tar and prepare the high-temperature compound gas stream. Preheat the raw oil to 140℃, and then send the high-temperature compound gas stream into the reaction furnace. The high-temperature compound gas stream and the coal tar are used as reaction raw materials.

[0138] (2) The high-temperature compound gas stream includes plasma jet, natural gas vortex, and air vortex. The temperature is about 3000℃, and the volume ratio of plasma jet:natural gas vortex:air vortex is 20:15:65.

[0139] (3) The oil and gas mixture in the throat pipe is introduced into the cracking zone, and the average temperature is 2000℃. The reaction residence time is 600ms, and the conductive carbon black and flue gas are rapidly cracked.

[0140] (4) The reaction furnace is supplied with cooling water to rapidly reduce the temperature and terminate the reaction.

[0141] (5) When the reaction furnace temperature drops to 250℃, the isobutyl alcohol esterified styrene-maleic anhydride dispersant aqueous solution (pH 8-10) mixed with the coal tar is introduced into the reaction furnace in a ratio of 0.33:1, which rapidly reduces the temperature and makes the superdispersant wrap around the surface of the carbon black. The cooled carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used for granulation to prepare carbon black particles. The isobutyl alcohol esterified styrene-maleic anhydride dispersant has Mn≈25000 (Suzhou Shiming Technology SUA-400), m:n=1:0.09, and the dispersant aqueous solution has a concentration of 15wt%. The structure of the dispersant is as follows:

[0142]

[0143] (6) The cooled conductive carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used for granulation to prepare conductive carbon black particles.

[0144] (7) The prepared conductive carbon black is placed in a 100℃ vacuum oven for drying treatment for 6h, and the PA6 resin powder is placed in a 100℃ vacuum oven for drying treatment for 5h.

[0145] (8) Then, the dried PA6 powder, conductive carbon black, and antioxidant are uniformly blended in a ratio of 69:30:1, and sequentially subjected to melt extrusion by a twin-screw extruder, water cooling granulation, and other processes to prepare a PA conductive master batch.

[0146] (9) Put the color master batch into a vacuum oven at 80℃, dry for 8-12h, and reduce the moisture content to below 50ppm. Then mix the PA6 fiber grade spinning chip according to a ratio of 1:4, melt spinning to prepare conductive nylon 6 fiber.

[0147] Example 10

[0148] (1) First, preheat the coal tar and prepare the high-temperature composite gas flow. Preheat the raw oil to 140℃, and then send the high-temperature composite gas flow into the reaction furnace. The high-temperature composite gas flow and the coal tar are used as reaction raw materials.

[0149] (2) The high-temperature composite gas flow includes plasma jet, natural gas vortex, and air vortex. The temperature is about 3000℃, and the volume ratio of plasma jet:natural gas vortex:air vortex is 20:15:65.

[0150] (3) The oil and gas mixed in the throat pipe are introduced into the cracking zone, and the average temperature is 2000℃. The reaction residence time is 600ms, and the conductive carbon black and flue gas are rapidly cracked.

[0151] (4) The cooling water is introduced into the reaction furnace to rapidly reduce the temperature and terminate the reaction.

[0152] (5) When the reaction furnace temperature drops to 250℃, the single-hydroxyl polycaprolactone type styrene-maleic anhydride dispersant aqueous solution (pH 8-10) mixed with the coal tar is introduced into the reaction furnace according to a mass ratio of 0.33:1, so that the temperature is rapidly reduced, and the super dispersant is wrapped on the surface of the carbon black. The cooled carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used for granulation, and then carbon black particles are prepared. The single-hydroxyl polycaprolactone type styrene-maleic anhydride dispersant has Mn≈25000, m:n=1:0.07 (Suzhou Shiming Technology SUA-500), and the dispersant aqueous solution has a concentration of 25wt%; the dispersant structure is as follows:

[0153]

[0154] (6) The cooled conductive carbon black and flue gas are separated and collected by a bag filter, and dry granulation is used for granulation, and then conductive carbon black particles are prepared.

[0155] (7) The prepared conductive carbon black is placed in a 100℃ vacuum oven for drying treatment for 6h, and the PA6 resin powder is placed in a 100℃ vacuum oven for drying treatment for 5h.

[0156] (8) Then the dry treated PA6 powder, conductive carbon black, antioxidant are blended uniformly according to the ratio of 69:30:1, and sequentially melt-extruded through a double screw extruder, water-cooled granulated, etc. to obtain PA conductive masterbatch.

[0157] (9) The color masterbatch is placed in a 80℃ vacuum oven and dried for 8-12h, the moisture content is reduced to below 50ppm, and then mixed uniformly with PA6 fiber grade spinning chip according to the ratio of 1:4, and melt-spun to obtain conductive nylon 6 fiber.

[0158] Example 11

[0159] (1) First, the coal tar is preheated and the high-temperature composite gas flow is prepared. The raw oil is preheated to 140℃, and then the high-temperature composite gas flow is sent into the reaction furnace. The high-temperature composite gas flow and the coal tar are used as reaction raw materials.

[0160] (2) The high-temperature composite gas flow includes plasma jet, natural gas vortex and air vortex. The temperature is about 3000℃, and the volume ratio of plasma jet:natural gas vortex:air vortex is 20:15:65.

[0161] (3) The oil gas mixed in the throat pipe is introduced into the cracking zone, and the average temperature is 2000℃. The reaction residence time is 600ms, and the conductive carbon black and flue gas are rapidly cracked.

[0162] (4) The cooling water is introduced into the reaction furnace to rapidly reduce the temperature and terminate the reaction.

[0163] (5) When the temperature of the reaction furnace is reduced to 250℃, the water solution mixed with ammonium polyacrylate (Mn≈5000) (concentration of 15wt%) is introduced into the reaction furnace to rapidly reduce the temperature and make the hyperdispersant wrapped on the surface of the carbon black. The carbon black and flue gas after cooling are separated and collected by a bag filter, and are granulated by a dry granulation method to obtain carbon black particles. The Mn of the ammonium polyacrylate is about 5000 (BASF BASF 4040) and the concentration is 15wt%; the structure of the dispersant is as follows:

[0164]

[0165] (6) The conductive carbon black and flue gas after cooling are separated and collected by a bag filter, and are granulated by a dry granulation method to obtain conductive carbon black particles.

[0166] (7) The prepared conductive carbon black is placed in a 100℃ vacuum oven for drying treatment for 6h, and the PA6 resin powder is placed in a 100℃ vacuum oven for drying treatment for 5h.

[0167] ​(8) The dried PA6 powder, conductive carbon black, and antioxidant were then evenly blended in a ratio of 69:30:1, and sequentially subjected to processes such as melt extrusion through a twin-screw extruder and water-cooled granulation to obtain PA conductive masterbatch.

[0168] (9) The masterbatch was placed in a vacuum oven at 80°C and dried for 8-12 hours until the moisture content was reduced to below 50 ppm. The masterbatch was then mixed evenly with PA6 fiber-grade spinning chips in a ratio of 1:4 and melt-spun to obtain conductive nylon 6 fibers.

[0169] Example 12

[0170] (1) First, the coal tar is preheated and the high-temperature composite airflow is prepared. The raw oil is preheated to 140°C, and then the high-temperature composite airflow is fed into the reactor. The high-temperature composite airflow and coal tar are used as reaction raw materials.

[0171] (2) The high-temperature composite airflow includes a plasma jet, a natural gas swirl, and an air swirl. The temperature is about 3000°C, and the volume ratio of the plasma jet: natural gas swirl: air swirl is 20:15:65.

[0172] (3) The oil and gas mixed in the throat are introduced into the cracking zone at an average temperature of 2000°C. The reaction residence time is 600ms, and the mixture is rapidly cracked to produce conductive carbon black and flue gas.

[0173] (4) Cooling water is introduced into the reactor to rapidly reduce its temperature and terminate the reaction.

[0174] (5) When the temperature of the reactor is reduced to 250°C, an aqueous solution mixed with sodium polyacrylate is introduced into the reactor at a mass ratio of 0.33:1 to coal tar, so that the temperature is rapidly reduced and the hyperdispersant is wrapped on the surface of the carbon black. The cooled carbon black and flue gas are separated and collected by a bag filter and granulated by dry granulation to obtain carbon black pellets. Among them, the Mn of sodium polyacrylate is ≈1000 (BASF 4141) concentration is 15wt%; the dispersant structure is as follows:

[0175]

[0176] (6) The conductive carbon black and flue gas after cooling are separated and collected by a bag filter. The conductive carbon black particles are granulated by dry granulation to obtain conductive carbon black particles.

[0177] (7) The prepared conductive carbon black was placed in a vacuum oven at 100°C and dried for 6 hours, and the PA6 resin powder was placed in a vacuum oven at 100°C and dried for 5 hours.

[0178] (8) The dried PA6 powder, conductive carbon black, and antioxidant were then evenly blended in a ratio of 69:30:1, and sequentially subjected to processes such as melt extrusion through a twin-screw extruder and water-cooled granulation to obtain PA conductive masterbatch.

[0179] (9) The masterbatch was placed in a vacuum oven at 80°C and dried for 8-12 hours until the moisture content was reduced to below 50 ppm. The masterbatch was then mixed evenly with PA6 fiber-grade spinning chips in a ratio of 1:4 and melt-spun to obtain conductive nylon 6 fibers.

[0180] Comparative Example 1

[0181] (1) First, the coal tar is preheated and the high-temperature composite airflow is prepared. The raw oil is preheated to 140°C, and then the high-temperature composite airflow is sent into the reactor. The high-temperature composite airflow and coal tar are used as reaction raw materials.

[0182] (2) The high-temperature composite airflow includes a plasma jet, a natural gas swirl, and an air swirl. The temperature is about 3000°C, and the volume ratio of the plasma jet: natural gas swirl: air swirl is 20:15:65.

[0183] (3) The oil and gas mixed in the throat are introduced into the cracking zone at an average temperature of 2000°C. The reaction residence time is 600ms, and the mixture is rapidly cracked to produce conductive carbon black and flue gas.

[0184] (4) Cooling water is introduced into the reactor to rapidly reduce its temperature and terminate the reaction.

[0185] (5) When the temperature of the reactor is reduced to 250° C., an aqueous solution mixed with sodium lignin sulfonate is introduced into the reactor at a mass ratio of 0.33:1 to coal tar, so that the temperature is rapidly reduced and the hyperdispersant is wrapped on the surface of the carbon black. The cooled carbon black and flue gas are separated and collected by a bag filter, and granulated by a dry granulation method to obtain carbon black pellets, wherein the concentration of the sodium lignin sulfonate aqueous solution is 15 wt%;

[0186] (6) The conductive carbon black and flue gas after cooling are separated and collected by a bag filter. The conductive carbon black particles are granulated by dry granulation to obtain conductive carbon black particles.

[0187] (7) The prepared conductive carbon black was placed in a vacuum oven at 100°C and dried for 6 hours, and the PA6 resin powder was placed in a vacuum oven at 100°C and dried for 5 hours.

[0188] (8) The dried PA6 powder, conductive carbon black, and antioxidant were then evenly blended in a ratio of 69:30:1, and sequentially subjected to processes such as melt extrusion through a twin-screw extruder and water-cooled granulation to obtain PA conductive masterbatch.

[0189] (9) The color master batch is placed in a vacuum oven at 80°C and dried for 8-12h, the moisture content is reduced to below 50ppm, and then mixed with PA6 fiber grade spinning chips at a ratio of 1:4, and melt spinning is performed to obtain conductive nylon 6 fibers.

[0190] Comparative Example 2

[0191] (1) First, the coal tar is preheated and the high-temperature compound gas flow is prepared, the raw oil is preheated to 140°C, and then the high-temperature compound gas flow is sent into the reaction furnace, and the high-temperature compound gas flow and the coal tar are used as reaction raw materials.

[0192] (2) The high-temperature compound gas flow includes plasma jet, natural gas cyclone and air cyclone. The temperature is about 3000°C, and the volume ratio of plasma jet:natural gas cyclone:air cyclone is 20:15:65.

[0193] (3) The oil gas mixed in the throat pipe is introduced into the cracking zone, and the average temperature is 2000°C. The reaction residence time is 600ms, and the conductive carbon black and flue gas are rapidly cracked.

[0194] (4) Cooling water is introduced into the reaction furnace to rapidly reduce the temperature and terminate the reaction. The conductive carbon black and flue gas after cooling are separated and collected by a bag filter. Dry granulation is used for granulation, and conductive carbon black particles are prepared.

[0195] (5) The prepared conductive carbon black is placed in a vacuum oven at 100°C and dried for 6h, and the PA6 resin powder is placed in a vacuum oven at 100°C and dried for 5h.

[0196] (6) Then, the dried PA6 powder, conductive carbon black and antioxidant are blended uniformly at a ratio of 69:30:1, and then sequentially subjected to melt extrusion by a twin-screw extruder, water cooling and granulation, to obtain a PA conductive master batch.

[0197] (7) The color master batch is placed in a vacuum oven at 80°C and dried for 8-12h, the moisture content is reduced to below 50ppm, and then mixed with PA6 fiber grade spinning chips at a ratio of 1:4, and melt spinning is performed to obtain conductive nylon 6 fibers.

[0198] Comparative Example 3

[0199] (1) The domestic conductive carbon black (Xinjiang Junxin Chemical Co., Ltd., model HPC115WB) is placed in a vacuum oven at 100°C and dried for 6h, and the PA6 resin powder is placed in a vacuum oven at 100°C and dried for 5h.

[0200] (2) Then the dry treated PA6 powder, conductive carbon black, antioxidant were blended uniformly according to the ratio of 69:30:1, and sequentially passed through the processes of melt extrusion by double screw extruder, water cooling granulation, etc. to prepare the PA conductive master batch.

[0201] (3) The color master batch was put into a vacuum oven at 80°C and dried for 8-12h, and the moisture content was reduced to below 50ppm. The PA6 fiber grade spinning chip was mixed uniformly according to the ratio of 1:4, and melt spinning was performed to prepare the conductive nylon 6 fiber.

[0202] Comparative Example 4

[0203] (1) The imported conductive carbon black (Cabot XC72) was dried in a vacuum oven at 100°C for 6h, and the PA6 resin powder was dried in a vacuum oven at 100°C for 5h.

[0204] (2) Then the dry treated PA6 powder, conductive carbon black, antioxidant were blended uniformly according to the ratio of 69:30:1, and sequentially passed through the processes of melt extrusion by double screw extruder, water cooling granulation, etc. to prepare the PA conductive master batch.

[0205] (3) The color master batch was put into a vacuum oven at 80°C and dried for 8-12h, and the moisture content was reduced to below 50ppm. The PA6 fiber grade spinning chip was mixed uniformly according to the ratio of 1:4, and melt spinning was performed to prepare the conductive nylon 6 fiber.

[0206] Table 1 Performance of conductive nylon 6 fiber of Examples 1-12 and Comparative Examples 1-4

[0207]

[0208] Note: Under the same process, the breaking strength of the nylon 6 fiber filament without carbon black is 4.48 cN / dtex.

[0209] It can be seen from the test results of Examples 1-6 that the conductive carbon black modified by the polyvinylpyrrolidone dispersant with medium molecular weight has good heat resistance and dispersibility, and meets the requirements of nylon 6 spinning. The molecular weight is low and it is easy to decompose at high temperature, but the molecular weight should not be too high, otherwise it will cause crosslinking and agglomeration in the system. It can be seen from the test results of Examples 7-8 that the filtering performance and conductivity are slightly poor at low concentration of dispersant, because the dispersant is difficult to completely wrap the carbon black, which makes the carbon black have poor dispersibility in nylon 6; but when the amount of dispersant is too much, it is easy to cause bridging and agglomeration in the nylon system. It can be seen from the test results of Examples 9-12 that the dispersibility in the nylon 6 system is poor when using styrene maleic anhydride copolymer and polyacrylate, because the compatibility of benzene-maleic resin and polyacrylic acid with polyamide is poor. Compared with Comparative Examples 1-4, the color master batch prepared by modifying the conductive carbon black with the polyvinylpyrrolidone dispersant with medium molecular weight in Examples 2-4 has low pressure filtration value, good spinnability, high conductivity, and the conductive nylon fiber prepared has high fiber breaking strength and conductivity.

[0210] The above provided examples are not intended to limit the scope covered by the present application, and the described steps are not intended to limit the execution order. The improvements of the present application made by those skilled in the art in combination with the existing common knowledge are also within the protection scope defined by the claims of the present application.

Claims

1. A method for preparing conductive nylon 6 fiber using modified conductive carbon black, characterized in that: The steps include: (1) Coal tar and high-temperature composite airflow are placed in a reaction furnace as reaction raw materials, wherein the high-temperature composite airflow includes plasma jet, natural gas swirl and air swirl, the temperature is 2000-4000°C, and the volume ratio of plasma jet: natural gas swirl: air swirl is 10-20:15-30:50-75; (2) introducing the oil and gas mixed in the throat into the cracking zone at an average temperature of 1800-2500°C and a reaction residence time of not less than 500ms to crack and generate conductive carbon black and flue gas. Water is introduced into the reactor to terminate the reaction. When the reactor temperature drops to 200-300°C, an aqueous solution mixed with a hyperdispersant is introduced into the reactor; (3) The conductive carbon black and flue gas after cooling are separated and collected by a bag filter, and granulated by a dry granulation method to obtain conductive carbon black pellets; (4) The dried PA6 powder, conductive carbon black particles, and processing aids are evenly blended in a certain proportion, and the PA conductive masterbatch is obtained through melt extrusion and water-cooling granulation. Finally, the PA conductive masterbatch is mixed with PA6 fiber-grade spinning chips and melt-spun to obtain conductive nylon 6 fibers.

2. The method according to claim 1, characterized in that In step (2), the hyperdispersant is one or more of polyvinyl pyrrolidone, modified polyacrylic acid, and styrene maleic anhydride copolymer.

3. The method according to claim 1, characterized in that In step (2), the structural formula of the polyvinyl pyrrolidone-based hyperdispersant is: Furthermore, the Mn of the polyvinyl pyrrolidone-based hyperdispersant is 8,000 to 1,300,000.

4. The method according to claim 1, wherein In step (2), the structural formula of the modified polyacrylic acid hyperdispersant is: Furthermore, R4 is one or more of sodium salt, ammonium salt, and potassium salt; and the Mn of the modified polyacrylic acid hyperdispersant is 1000 to 5000.

5. The method according to claim 1, wherein In step (2), the structural formula of the styrene-maleic anhydride copolymer hyperdispersant is: Among them, m:n is 1:0.03 to 1:0.15; R1 is one of OH, alkylhydroxyl, and polyester hydroxyl groups; R2 is one of OH, alkylhydroxyl, and polyester hydroxyl groups; and the Mn of the styrene-maleic anhydride copolymer hyperdispersant is 10,000-40,000.

6. The method according to claim 1, characterized in that In step (2), the mass fraction of the hyperdispersant aqueous solution is 5-25%.

7. The method according to claim 1, characterized in that In step (4), in the PA conductive masterbatch, the mass fraction of conductive carbon black is 25%-35%, the mass fraction of PA6 powder is 65%-75%, and the mass fraction of processing aid is 1%-3%.

8. The method according to claim 1, characterized in that In step (4), the processing aid is an antioxidant.

9. The method according to claim 8, characterized in that The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or a phosphite antioxidant.

10. Conductive nylon 6 fiber prepared by the method according to any one of claims 1 to 9.

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