Light-absorbing heat-generating nylon fiber and method for preparing the same

Abstract

The application provides a light-absorbing and heat-generating nylon fiber and a preparation method thereof, relates to the technical field of fibers, and uses KH560 modified TiN / carbon composite material as a light-absorbing and heat-generating additive and uses anti-aging agent modified butyronitrile rubber as a toughening agent, so that chemical bonds are formed between the components and a PA6 matrix in a molten state, the compatibility and dispersibility of the components are improved, the light-absorbing and heat-generating characteristics of the nylon fiber are endowed, and the aging resistance and toughness of the fiber are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fibers, in particular to a light-absorbing and heat-releasing nylon fiber and a preparation method thereof. BACKGROUND

[0002] Polyamide 6 (PA6) fibers are widely used in the field of clothing textiles due to their good moisture absorption, softness, skin-friendliness, and resilience. Light-absorbing and heat-releasing far-infrared fibers are a kind of organic / inorganic hybrid functional fibers that utilize the high-efficiency absorption of inorganic nanoparticles in the visible and near-infrared light bands and the high radiation capacity of far-infrared to enhance the functionality of organic fiber composites. Light-absorbing and heat-releasing far-infrared fibers achieve the function of thermal insulation through a two-way thermal insulation mechanism, which is embodied in the following aspects: about 60% of the heat of the human body is lost through thermal radiation, and more than 80% of the energy of solar radiation is concentrated in the visible and near-infrared light bands. The functional powder introduced into the fiber absorbs the radiation energy in these bands and converts it into heat energy, which is stored inside the fabric, thereby reducing the heat exchange between the human body and the environment and achieving the effect of active heating. At the same time, the fiber reflects the far-infrared radiation of the human body itself, effectively inhibiting heat loss and forming a two-way thermal insulation mechanism.

[0003] Currently, the main methods for introducing light-absorbing and heat-releasing far-infrared powder into PA6 fibers to enhance their functionality are melt blending, solution blending, and in-situ polymerization. Although the melt blending method has a simple production process and high research and development efficiency, the inorganic nanoparticles cannot be uniformly distributed in the fiber matrix during blending, leading to unstable spinning process and decreased product performance. The solution blending method and the in-situ polymerization method overcome the poor dispersion of inorganic nanoparticles in the matrix, but have low production efficiency. In addition, nylon fibers, as high polymer resin-based materials, also have the problem of insufficient anti-aging performance.

[0004] Therefore, in view of the deficiencies of the prior art, it is necessary to design a light-absorbing and heat-releasing nylon fiber that not only imparts the fiber with light-absorbing and heat-releasing properties but also improves the anti-aging performance of the fiber. SUMMARY

[0005] To overcome the deficiencies in the prior art, the present application aims to provide a light-absorbing and heat-releasing nylon fiber and a preparation method thereof. By using KH560-modified TiN / carbon composite material as a light-absorbing and heat-releasing additive and anti-aging agent-modified nitrile rubber as a toughening agent, chemical bonds are formed between the components and the PA6 matrix in the molten state, thereby improving the compatibility and dispersion of the components. This not only imparts the nylon fiber with light-absorbing and heat-releasing properties but also improves the anti-aging and toughness of the fiber.

[0006] To achieve the above and other related purposes, the technical solution provided by the present application is as follows:

[0007] A method for preparing light-absorbing and heat-generating nylon fibers includes the following steps:

[0008] Step (1): Mix 4,4'-diaminodiphenylamine, ethanol, and the catalyst dibutyltin dilaurate evenly, add allyl isothiocyanate dropwise, react, precipitate, filter, wash, and dry to obtain the reactive antioxidant.

[0009] Step (2): Mix water, emulsifier, stabilizer and acrylonitrile, add reactive antioxidant and butadiene, then add redox initiator, chelating agent and molecular weight regulator, react, after the reaction is completed, degas and condense, dry to obtain modified nitrile rubber;

[0010] Step (3): Mix TiN / carbon composite material, KH560 and isopropanol, stir and treat, filter, wash and dry after treatment to obtain light-absorbing and heat-generating additive;

[0011] Light-absorbing and heat-generating additives and modified nitrile rubber were added to PA6 chips in sequence, melt-blended, extruded and pelletized to obtain light-absorbing and heat-generating masterbatch.

[0012] The light-absorbing and heat-generating masterbatch was blended with PA6 chips, melt-spun, cooled and stretched to obtain light-absorbing and heat-generating nylon fibers.

[0013] The preferred technical solution is that in step (1): the molar ratio of 4,4'-diaminodiphenylamine and allyl isothiocyanate is 1:1-1.3; the solid-liquid ratio of 4,4'-diaminodiphenylamine, ethanol and catalyst dibutyltin dilaurate is 10g:60-100mL:0.05-0.08g; the reaction conditions are: react at 45-55℃ for 4-6h, and after the reaction is completed, cool down to 20-25℃ and continue to react for 48h.

[0014] The preferred technical solution is that, in step (2), the mass ratio of acrylonitrile, butadiene, water, emulsifier, stabilizer, reactive antioxidant, redox initiator, chelating agent, and molecular weight regulator is 20-30:70-80:200-300:5-5.5:0.005-0.006:2-3:0.2-0.3:0.03:0.4-0.5; the conditions for adding the redox initiator, chelating agent, and molecular weight regulator are: adding them in a nitrogen atmosphere at a temperature of 5-15℃; and the reaction conditions are: reacting at a temperature of 5-30℃ for 7-12 hours.

[0015] The preferred technical solution is that in step (2): the emulsifier is prepared by mixing potassium rosinate soap and sodium β-naphthalenesulfonate formaldehyde condensate in a mass ratio of 10-15:1; in the redox initiator, the mass ratio of dicumyl peroxide, sodium iron ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and sodium bisulfite is 8-10:0.5-1:8-10:2-3.

[0016] The preferred technical solution is that, in step (3), the TiN / carbon composite material is prepared by the following steps:

[0017] Xylose, acetic acid, TiN, and water were mixed in a mass ratio of 25:15:1.5-2:400-600 and reacted at 190-220℃ for 3-7 hours. After the reaction was completed, the mixture was cooled to room temperature, the precipitate was collected by filtration, washed with water and ethanol, and dried to obtain the TiN / carbon composite material.

[0018] The preferred technical solution is that in step (3), the solid-liquid ratio of TiN / carbon composite material, KH560 and isopropanol is 10g:0.3-1g:300-400mL; the reaction conditions are: stirring at 55-65℃ for 1.5-3h.

[0019] The preferred technical solution is that in step (3): the mass ratio of light-absorbing and heat-generating additive, modified nitrile rubber, and PA6 chips is 1-2:10-20:80-90; the melt spinning conditions are: temperature in zone 1 270-280℃, zone 2 295-297℃, and zones 3 to 4 290-292℃, spinning speed is 800-1000m / min; and the draw ratio is 3-3.8 times.

[0020] The preferred technical solution is a light-absorbing and heat-generating nylon fiber prepared by the light-absorbing and heat-generating nylon fiber preparation method described above.

[0021] Due to the application of the above technical solution, the beneficial effects of this invention are as follows:

[0022] 1. This invention uses KH560 modified TiN / carbon composite material as light-absorbing and heat-generating additive and antioxidant modified nitrile rubber as toughening agent. By utilizing the chemical bonds formed between each component and PA6 matrix in the molten state, the compatibility and dispersibility of each component are improved. This not only endows nylon fiber with light-absorbing and heat-generating properties, but also improves the fiber's aging resistance and toughness.

[0023] 2. In this invention, a reactive antioxidant with an amino, aromatic secondary amine, thiourea, and allyl structure is synthesized by reacting 4,4'-diaminodiphenylamine with allyl isothiocyanate. The -NH- group can capture and passivate oxygen free radicals, and the thiourea group can effectively decompose hydrogen peroxide. These two components synergistically improve the anti-aging performance of the material, while the allyl structure can participate in the polymerization reaction of nitrile rubber. This invention introduces the reactive antioxidant as a monomer into the polymerization process of nitrile rubber. Due to the use of a low-temperature redox initiation system for the polymerization reaction, the polymerization rate is increased. The resulting modified nitrile rubber contains the antioxidant component, effectively improving the material's aging resistance.

[0024] 3. This invention utilizes the synergistic effect of TiN and carbon materials in photothermal conversion performance. Using xylose as the carbon source and acetic acid as the catalyst, the hydrothermal method is used to introduce TiN materials into carbon materials, producing a TiN / carbon composite material with better light absorption and heat generation performance. Then, KH560 is used to modify its surface to produce a light absorption and heat generation additive containing epoxy functional groups. Through the chemical bond formed by the reaction between epoxy groups and amino groups in modified nitrile rubber, terminal hydroxyl groups and terminal carboxyl groups in PA6 under molten conditions, not only is the compatibility between the light absorption and heat generation additive, modified nitrile rubber and PA6 improved, but the aging resistance and toughness of the light absorption and heat generation nylon fiber are also improved. Attached Figure Description

[0025] Figure 1 The bar chart shows the breaking strength retention rate of the light-absorbing and heat-generating nylon fibers prepared in Examples 1-5 and Comparative Examples 1-3 of this invention during performance testing.

[0026] Figure 2 This is a temperature difference graph of samples 1-8 prepared from Examples 1-5 and Comparative Examples 1-3 during performance testing.

[0027] Figure 3 This is a schematic diagram of the reaction for preparing the reactive antioxidant in this invention. Detailed Implementation

[0028] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification.

[0029] Please see Figures 1-3It should be noted that in the description of this invention, the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product is in use. These terms are used only for the convenience of describing the invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the invention. Furthermore, the terms "first," "second," and "third," etc., are only used to distinguish descriptions and should not be construed as indicating or implying relative importance. The terms "horizontal," "vertical," and "suspended," etc., do not indicate that the component must be absolutely horizontal or suspended, but can be slightly tilted. For example, "horizontal" simply means that its direction is more horizontal than "vertical," and does not mean that the structure must be completely horizontal, but can be slightly tilted.

[0030] In the description of this invention, it should also be noted that, unless otherwise explicitly specified and limited, the terms "set," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal communication between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0031] Example 1

[0032] This embodiment discloses a method for preparing light-absorbing and heat-generating nylon fibers, including the following steps:

[0033] Step (1): Mix 4,4'-diaminodiphenylamine, ethanol, and dibutyltin dilaurate catalyst at a solid-liquid ratio of 10g:60mL:0.06g. Add allyl isothiocyanate dropwise over 30 minutes. After the addition is complete, heat to 45℃ and react for 4 hours. After the reaction is complete, cool to 25℃ and continue the reaction for 48 hours. After the reaction is complete, add cyclohexane to precipitate the precipitate. Filter the precipitate, wash it with cyclohexane, and dry it at 40℃ for 12 hours to obtain the reactive antioxidant.

[0034] The molar ratio of 4,4'-diaminodiphenylamine to allyl isothiocyanate is 1:1.

[0035] Step (2): Mix water, emulsifier, stabilizer and acrylonitrile, add reactive antioxidant and butadiene in a nitrogen atmosphere, add redox initiator, chelating agent and molecular weight regulator at 5°C, react at 8°C for 10 hours, after the reaction is completed, degas and condense, dry with hot air to obtain modified nitrile rubber.

[0036] The mass ratio of acrylonitrile, butadiene, water, emulsifier, stabilizer, reactive antioxidant, redox initiator, chelating agent, and molecular weight regulator is 27:73:200:5.2:0.006:2:0.2:0.03:0.48.

[0037] The emulsifier is prepared by mixing potassium rosinate soap and sodium β-naphthalenesulfonate formaldehyde condensate in a mass ratio of 13:1; the redox initiator has a mass ratio of dicumyl peroxide, sodium iron ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and sodium bisulfite of 8:1:8:3.

[0038] Step (3): Mix xylose, acetic acid, TiN and water in a mass ratio of 25:15:1.5:500 and react at 200℃ for 4 hours. After the reaction is completed, cool down to room temperature, filter to collect the precipitate, wash with water and ethanol, and dry at 60℃ for 12 hours to obtain TiN / carbon composite material.

[0039] TiN / carbon composite material, KH560, and isopropanol were mixed at a solid-liquid ratio of 10g:0.3g:300mL and stirred at 60℃ for 1.5h. After treatment, the mixture was filtered, washed, and dried to obtain a light-absorbing and heat-generating additive.

[0040] Light-absorbing and heat-generating additives and modified nitrile rubber were added to PA6 chips in sequence, melt-blended at 250°C, extruded and pelletized to obtain light-absorbing and heat-generating masterbatch.

[0041] The light-absorbing and heat-generating masterbatch was blended with PA6 chips, melt-spun, cooled and drawn to obtain light-absorbing and heat-generating nylon fibers.

[0042] The mass ratio of light-absorbing and heat-generating additive, modified nitrile rubber, and PA6 chips is 1:10:90; the melt spinning conditions are: 275℃ in zone 1, 297℃ in zone 2, and 292℃ in zones 3 to 4, with a spinning speed of 800m / min and a draw ratio of 3.8.

[0043] Example 2

[0044] This embodiment discloses a method for preparing light-absorbing and heat-generating nylon fibers, including the following steps:

[0045] Step (1): Mix 4,4'-diaminodiphenylamine, ethanol, and dibutyltin dilaurate catalyst at a solid-liquid ratio of 10g:60mL:0.06g. Add allyl isothiocyanate dropwise over 30 minutes. After the addition is complete, heat to 45℃ and react for 4 hours. After the reaction is complete, cool to 25℃ and continue the reaction for 48 hours. After the reaction is complete, add cyclohexane to precipitate the precipitate. Filter the precipitate, wash it with cyclohexane, and dry it at 40℃ for 12 hours to obtain the reactive antioxidant.

[0046] The molar ratio of 4,4'-diaminodiphenylamine to allyl isothiocyanate is 1:1.

[0047] Step (2): Mix water, emulsifier, stabilizer and acrylonitrile, add reactive antioxidant and butadiene in a nitrogen atmosphere, add redox initiator, chelating agent and molecular weight regulator at 5°C, react at 8°C for 10 hours, after the reaction is completed, degas and condense, dry with hot air to obtain modified nitrile rubber.

[0048] The mass ratio of acrylonitrile, butadiene, water, emulsifier, stabilizer, reactive antioxidant, redox initiator, chelating agent, and molecular weight regulator is 27:73:200:5.2:0.006:2.3:0.2:0.03:0.48.

[0049] The emulsifier is prepared by mixing potassium rosinate soap and sodium β-naphthalenesulfonate formaldehyde condensate in a mass ratio of 13:1; the redox initiator has a mass ratio of dicumyl peroxide, sodium iron ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and sodium bisulfite of 8:1:8:3.

[0050] Step (3): Mix xylose, acetic acid, TiN and water in a mass ratio of 25:15:1.6:500 and react at 200℃ for 4 hours. After the reaction is completed, cool down to room temperature, filter to collect the precipitate, wash with water and ethanol, and dry at 60℃ for 12 hours to obtain TiN / carbon composite material.

[0051] TiN / carbon composite material, KH560, and isopropanol were mixed at a solid-liquid ratio of 10g:0.3g:300mL and stirred at 60℃ for 1.5h. After treatment, the mixture was filtered, washed, and dried to obtain a light-absorbing and heat-generating additive.

[0052] Light-absorbing and heat-generating additives and modified nitrile rubber were added to PA6 chips in sequence, melt-blended at 250°C, extruded and pelletized to obtain light-absorbing and heat-generating masterbatch.

[0053] The light-absorbing and heat-generating masterbatch was blended with PA6 chips, melt-spun, cooled and drawn to obtain light-absorbing and heat-generating nylon fibers.

[0054] The mass ratio of light-absorbing and heat-generating additive, modified nitrile rubber, and PA6 chips is 1.3:12:88; the melt spinning conditions are: temperature in zone 1 275℃, zone 2 297℃, and zones 3 to 4 292℃, spinning speed 800m / min; and draw ratio 3.8.

[0055] Example 3

[0056] This embodiment discloses a method for preparing light-absorbing and heat-generating nylon fibers, including the following steps:

[0057] Step (1): Mix 4,4'-diaminodiphenylamine, ethanol, and dibutyltin dilaurate catalyst at a solid-liquid ratio of 10g:60mL:0.06g. Add allyl isothiocyanate dropwise over 30 minutes. After the addition is complete, heat to 45℃ and react for 4 hours. After the reaction is complete, cool to 25℃ and continue the reaction for 48 hours. After the reaction is complete, add cyclohexane to precipitate the precipitate. Filter the precipitate, wash it with cyclohexane, and dry it at 40℃ for 12 hours to obtain the reactive antioxidant.

[0058] The molar ratio of 4,4'-diaminodiphenylamine to allyl isothiocyanate is 1:1.

[0059] Step (2): Mix water, emulsifier, stabilizer and acrylonitrile, add reactive antioxidant and butadiene in a nitrogen atmosphere, add redox initiator, chelating agent and molecular weight regulator at 5°C, react at 8°C for 10 hours, after the reaction is completed, degas and condense, dry with hot air to obtain modified nitrile rubber.

[0060] The mass ratio of acrylonitrile, butadiene, water, emulsifier, stabilizer, reactive antioxidant, redox initiator, chelating agent, and molecular weight regulator is 27:73:200:5.2:0.006:2.5:0.2:0.03:0.48.

[0061] The emulsifier is prepared by mixing potassium rosinate soap and sodium β-naphthalenesulfonate formaldehyde condensate in a mass ratio of 13:1; the redox initiator has a mass ratio of dicumyl peroxide, sodium iron ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and sodium bisulfite of 8:1:8:3.

[0062] Step (3): Mix xylose, acetic acid, TiN and water in a mass ratio of 25:15:1.8:500 and react at 200℃ for 4 hours. After the reaction is completed, cool down to room temperature, filter to collect the precipitate, wash with water and ethanol, and dry at 60℃ for 12 hours to obtain TiN / carbon composite material.

[0063] TiN / carbon composite material, KH560, and isopropanol were mixed at a solid-liquid ratio of 10g:0.3g:300mL and stirred at 60℃ for 1.5h. After treatment, the mixture was filtered, washed, and dried to obtain a light-absorbing and heat-generating additive.

[0064] Light-absorbing and heat-generating additives and modified nitrile rubber were added to PA6 chips in sequence, melt-blended at 250°C, extruded and pelletized to obtain light-absorbing and heat-generating masterbatch.

[0065] The light-absorbing and heat-generating masterbatch was blended with PA6 chips, melt-spun, cooled and drawn to obtain light-absorbing and heat-generating nylon fibers.

[0066] The mass ratio of light-absorbing and heat-generating additive, modified nitrile rubber, and PA6 chips is 1.5:15:85; the melt spinning conditions are: 275℃ in zone 1, 297℃ in zone 2, and 292℃ in zones 3 to 4, with a spinning speed of 800m / min and a draw ratio of 3.8.

[0067] Example 4

[0068] This embodiment discloses a method for preparing light-absorbing and heat-generating nylon fibers, including the following steps:

[0069] Step (1): Mix 4,4'-diaminodiphenylamine, ethanol, and dibutyltin dilaurate catalyst at a solid-liquid ratio of 10g:60mL:0.06g. Add allyl isothiocyanate dropwise over 30 minutes. After the addition is complete, heat to 45℃ and react for 4 hours. After the reaction is complete, cool to 25℃ and continue the reaction for 48 hours. After the reaction is complete, add cyclohexane to precipitate the precipitate. Filter the precipitate, wash it with cyclohexane, and dry it at 40℃ for 12 hours to obtain the reactive antioxidant.

[0070] The molar ratio of 4,4'-diaminodiphenylamine to allyl isothiocyanate is 1:1.

[0071] Step (2): Mix water, emulsifier, stabilizer and acrylonitrile, add reactive antioxidant and butadiene in a nitrogen atmosphere, add redox initiator, chelating agent and molecular weight regulator at 5°C, react at 8°C for 10 hours, after the reaction is completed, degas and condense, dry with hot air to obtain modified nitrile rubber.

[0072] The mass ratio of acrylonitrile, butadiene, water, emulsifier, stabilizer, reactive antioxidant, redox initiator, chelating agent, and molecular weight regulator is 27:73:200:5.2:0.006:2.8:0.2:0.03:0.48.

[0073] The emulsifier is prepared by mixing potassium rosinate soap and sodium β-naphthalenesulfonate formaldehyde condensate in a mass ratio of 13:1; the redox initiator has a mass ratio of dicumyl peroxide, sodium iron ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and sodium bisulfite of 8:1:8:3.

[0074] Step (3): Mix xylose, acetic acid, TiN and water in a mass ratio of 25:15:1.9:500 and react at 200℃ for 4 hours. After the reaction is completed, cool down to room temperature, filter to collect the precipitate, wash with water and ethanol, and dry at 60℃ for 12 hours to obtain TiN / carbon composite material.

[0075] TiN / carbon composite material, KH560, and isopropanol were mixed at a solid-liquid ratio of 10g:0.3g:300mL and stirred at 60℃ for 1.5h. After treatment, the mixture was filtered, washed, and dried to obtain a light-absorbing and heat-generating additive.

[0076] Light-absorbing and heat-generating additives and modified nitrile rubber were added to PA6 chips in sequence, melt-blended at 250°C, extruded and pelletized to obtain light-absorbing and heat-generating masterbatch.

[0077] The light-absorbing and heat-generating masterbatch was blended with PA6 chips, melt-spun, cooled and drawn to obtain light-absorbing and heat-generating nylon fibers.

[0078] The mass ratio of light-absorbing and heat-generating additive, modified nitrile rubber, and PA6 chips is 1.8:18:82; the melt spinning conditions are: 275℃ in zone 1, 297℃ in zone 2, and 292℃ in zones 3 to 4, with a spinning speed of 800m / min and a draw ratio of 3.8.

[0079] Example 5

[0080] This embodiment discloses a method for preparing light-absorbing and heat-generating nylon fibers, including the following steps:

[0081] Step (1): Mix 4,4'-diaminodiphenylamine, ethanol, and dibutyltin dilaurate catalyst at a solid-liquid ratio of 10g:60mL:0.06g. Add allyl isothiocyanate dropwise over 30 minutes. After the addition is complete, heat to 45℃ and react for 4 hours. After the reaction is complete, cool to 25℃ and continue the reaction for 48 hours. After the reaction is complete, add cyclohexane to precipitate the precipitate. Filter the precipitate, wash it with cyclohexane, and dry it at 40℃ for 12 hours to obtain the reactive antioxidant.

[0082] The molar ratio of 4,4'-diaminodiphenylamine to allyl isothiocyanate is 1:1.

[0083] Step (2): Mix water, emulsifier, stabilizer and acrylonitrile, add reactive antioxidant and butadiene in a nitrogen atmosphere, add redox initiator, chelating agent and molecular weight regulator at 5°C, react at 8°C for 10 hours, after the reaction is completed, degas and condense, dry with hot air to obtain modified nitrile rubber.

[0084] The mass ratio of acrylonitrile, butadiene, water, emulsifier, stabilizer, reactive antioxidant, redox initiator, chelating agent, and molecular weight regulator is 27:73:200:5.2:0.006:3:0.2:0.03:0.48.

[0085] The emulsifier is prepared by mixing potassium rosinate soap and sodium β-naphthalenesulfonate formaldehyde condensate in a mass ratio of 13:1; the redox initiator has a mass ratio of dicumyl peroxide, sodium iron ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and sodium bisulfite of 8:1:8:3.

[0086] Step (3): Mix xylose, acetic acid, TiN and water in a mass ratio of 25:15:2:500 and react at 200℃ for 4 hours. After the reaction is completed, cool down to room temperature, filter to collect the precipitate, wash with water and ethanol, and dry at 60℃ for 12 hours to obtain TiN / carbon composite material.

[0087] TiN / carbon composite material, KH560, and isopropanol were mixed at a solid-liquid ratio of 10g:0.3g:300mL and stirred at 60℃ for 1.5h. After treatment, the mixture was filtered, washed, and dried to obtain a light-absorbing and heat-generating additive.

[0088] Light-absorbing and heat-generating additives and modified nitrile rubber were added to PA6 chips in sequence, melt-blended at 250°C, extruded and pelletized to obtain light-absorbing and heat-generating masterbatch.

[0089] The light-absorbing and heat-generating masterbatch was blended with PA6 chips, melt-spun, cooled and drawn to obtain light-absorbing and heat-generating nylon fibers.

[0090] The mass ratio of light-absorbing and heat-generating additive, modified nitrile rubber, and PA6 chips is 2:20:80; the melt spinning conditions are: 275℃ in zone 1, 297℃ in zone 2, and 292℃ in zones 3 to 4, with a spinning speed of 800m / min and a draw ratio of 3.8.

[0091] Comparative Example 1

[0092] This comparative example discloses a method for preparing light-absorbing and heat-generating nylon fibers, including the following steps:

[0093] Step (1): Mix water, emulsifier, stabilizer and acrylonitrile, add butadiene in a nitrogen atmosphere, add redox initiator, chelating agent and molecular weight regulator at 5°C, react at 8°C for 10 hours, after the reaction is completed, degas and condense, dry with hot air to obtain nitrile rubber.

[0094] The mass ratio of acrylonitrile, butadiene, water, emulsifier, stabilizer, redox initiator, chelating agent, and molecular weight regulator is 27:73:200:5.2:0.006:0.2:0.03:0.48.

[0095] The emulsifier is prepared by mixing potassium rosinate soap and sodium β-naphthalenesulfonate formaldehyde condensate in a mass ratio of 13:1; the redox initiator has a mass ratio of dicumyl peroxide, sodium iron ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and sodium bisulfite of 8:1:8:3.

[0096] Step (3): Mix xylose, acetic acid, TiN and water in a mass ratio of 25:15:1.5:500 and react at 200℃ for 4 hours. After the reaction is completed, cool down to room temperature, filter to collect the precipitate, wash with water and ethanol, and dry at 60℃ for 12 hours to obtain TiN / carbon composite material.

[0097] TiN / carbon composite material, KH560, and isopropanol were mixed at a solid-liquid ratio of 10g:0.3g:300mL and stirred at 60℃ for 1.5h. After treatment, the mixture was filtered, washed, and dried to obtain a light-absorbing and heat-generating additive.

[0098] Light-absorbing and heat-generating additives and nitrile rubber were added to PA6 chips in sequence, melt-blended at 250°C, and extruded into pellets to obtain light-absorbing and heat-generating masterbatch.

[0099] The light-absorbing and heat-generating masterbatch was blended with PA6 chips, melt-spun, cooled and drawn to obtain light-absorbing and heat-generating nylon fibers.

[0100] The mass ratio of light-absorbing and heat-generating additive, nitrile rubber, and PA6 chips is 1:10:90; the melt spinning conditions are: 275℃ in zone 1, 297℃ in zone 2, and 292℃ in zones 3 to 4, with a spinning speed of 800m / min and a draw ratio of 3.8.

[0101] Comparative Example 2

[0102] This comparative example discloses a method for preparing light-absorbing and heat-generating nylon fibers, including the following steps:

[0103] Step (1): Mix 4,4'-diaminodiphenylamine, ethanol, and dibutyltin dilaurate catalyst at a solid-liquid ratio of 10g:60mL:0.06g. Add allyl isothiocyanate dropwise over 30 minutes. After the addition is complete, heat to 45℃ and react for 4 hours. After the reaction is complete, cool to 25℃ and continue the reaction for 48 hours. After the reaction is complete, add cyclohexane to precipitate the precipitate. Filter the precipitate, wash it with cyclohexane, and dry it at 40℃ for 12 hours to obtain the reactive antioxidant.

[0104] The molar ratio of 4,4'-diaminodiphenylamine to allyl isothiocyanate is 1:1.

[0105] Step (2): Mix water, emulsifier, stabilizer and acrylonitrile, add reactive antioxidant and butadiene in a nitrogen atmosphere, add redox initiator, chelating agent and molecular weight regulator at 5°C, react at 8°C for 10 hours, after the reaction is completed, degas and condense, dry with hot air to obtain modified nitrile rubber.

[0106] The mass ratio of acrylonitrile, butadiene, water, emulsifier, stabilizer, reactive antioxidant, redox initiator, chelating agent, and molecular weight regulator is 27:73:200:5.2:0.006:2:0.2:0.03:0.48.

[0107] The emulsifier is prepared by mixing potassium rosinate soap and sodium β-naphthalenesulfonate formaldehyde condensate in a mass ratio of 13:1; the redox initiator has a mass ratio of dicumyl peroxide, sodium iron ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and sodium bisulfite of 8:1:8:3.

[0108] Step (3): Mix xylose, acetic acid, TiN and water in a mass ratio of 25:15:1.5:500 and react at 200℃ for 4 hours. After the reaction is completed, cool down to room temperature, filter to collect the precipitate, wash with water and ethanol, and dry at 60℃ for 12 hours to obtain TiN / carbon composite material.

[0109] TiN / carbon composite material and modified nitrile rubber were sequentially added to PA6 chips, melt-blended at 250℃, extruded and pelletized to obtain light-absorbing and heat-generating masterbatch;

[0110] The light-absorbing and heat-generating masterbatch was blended with PA6 chips, melt-spun, cooled and drawn to obtain light-absorbing and heat-generating nylon fibers.

[0111] The mass ratio of TiN / carbon composite material, modified nitrile rubber, and PA6 chips is 1:10:90; the melt spinning conditions are: 275℃ in zone 1, 297℃ in zone 2, and 292℃ in zones 3 to 4, with a spinning speed of 800m / min and a draw ratio of 3.8.

[0112] Comparative Example 3

[0113] This comparative example discloses a method for preparing light-absorbing and heat-generating nylon fibers, including the following steps:

[0114] Step (1): Mix 4,4'-diaminodiphenylamine, ethanol, and dibutyltin dilaurate catalyst at a solid-liquid ratio of 10g:60mL:0.06g. Add allyl isothiocyanate dropwise over 30 minutes. After the addition is complete, heat to 45℃ and react for 4 hours. After the reaction is complete, cool to 25℃ and continue the reaction for 48 hours. After the reaction is complete, add cyclohexane to precipitate the precipitate. Filter the precipitate, wash it with cyclohexane, and dry it at 40℃ for 12 hours to obtain the reactive antioxidant.

[0115] The molar ratio of 4,4'-diaminodiphenylamine to allyl isothiocyanate is 1:1.

[0116] Step (2): Mix water, emulsifier, stabilizer and acrylonitrile, add reactive antioxidant and butadiene in a nitrogen atmosphere, add redox initiator, chelating agent and molecular weight regulator at 5°C, react at 8°C for 10 hours, after the reaction is completed, degas and condense, dry with hot air to obtain modified nitrile rubber.

[0117] The mass ratio of acrylonitrile, butadiene, water, emulsifier, stabilizer, reactive antioxidant, redox initiator, chelating agent, and molecular weight regulator is 27:73:200:5.2:0.006:2:0.2:0.03:0.48.

[0118] The emulsifier is prepared by mixing potassium rosinate soap and sodium β-naphthalenesulfonate formaldehyde condensate in a mass ratio of 13:1; the redox initiator has a mass ratio of dicumyl peroxide, sodium iron ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and sodium bisulfite of 8:1:8:3.

[0119] Step (3): Mix xylose, acetic acid and water in a mass ratio of 25:15:500 and react at 200℃ for 4 hours. After the reaction is complete, cool down to room temperature, filter to collect the precipitate, wash with water and ethanol, and dry at 60℃ for 12 hours to obtain carbon material.

[0120] Carbon material, KH560, and isopropanol were mixed at a solid-liquid ratio of 10g:0.3g:300mL and stirred at 60℃ for 1.5h. After the treatment was completed, the mixture was filtered, washed, and dried to obtain a light-absorbing and heat-generating additive.

[0121] Light-absorbing and heat-generating additives and modified nitrile rubber were added to PA6 chips in sequence, melt-blended at 250°C, extruded and pelletized to obtain light-absorbing and heat-generating masterbatch.

[0122] The light-absorbing and heat-generating masterbatch was blended with PA6 chips, melt-spun, cooled and drawn to obtain light-absorbing and heat-generating nylon fibers.

[0123] The mass ratio of light-absorbing and heat-generating additive, modified nitrile rubber, and PA6 chips is 1:10:90; the melt spinning conditions are: 275℃ in zone 1, 297℃ in zone 2, and 292℃ in zones 3 to 4, with a spinning speed of 800m / min and a draw ratio of 3.8.

[0124] In the above examples and comparative examples: xylose was commercially available; TiN had a particle size of 30-100 nm; the stabilizer was potassium phosphate; the chelating agent was tetrasodium ethylenediaminetetraacetate; the molecular weight regulator was tert-dodecyl mercaptan; and the PA6 chips were fiber-grade PA6 chips.

[0125] Test case

[0126] The light-absorbing and heat-generating nylon fibers prepared in Examples 1-5 and Comparative Examples 1-3 were tested for mechanical properties and aging resistance. The light-absorbing and heat-generating nylon fibers prepared in Examples 1-5 and Comparative Examples 1-3 were processed to a basis weight of 150 g / m². 2 The fabrics, designated as samples 1-8, were subjected to light absorption and heat generation performance tests. The specific test results are shown in Tables 1 and 2.

[0127] Table 1

[0128] Breaking strength (cN / dtex) Breaking strength retention (%) Example 1 3.9 94.6 Example 2 4.0 95.1 Example 3 4.0 95.5 Example 4 4.2 95.9 Example 5 4.3 96.3 Comparative Example 1 3.9 71.5 Comparative Example 2 3.2 94.5 Comparative Example 3 4.0 94.6

[0129] Table 2

[0130] Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Temperature difference (°C) 22.3 23.1 23.8 24.6 25.3 22.3 22.1 18.2

[0131] The tests for each indicator in Tables 1 and 2 were conducted according to the following standards: Tensile strength was determined according to GB / T14344-2008 "Test Method for Tensile Properties of Chemical Fiber Filaments"; aging resistance was expressed by the retention rate of tensile strength, and the test method was as follows: fibers prepared in Examples 1-5 and Comparative Examples 1-3 were suspended in an aging test chamber, the test temperature was set to 85℃, and aging was continued for 100 hours; light absorption and heat generation performance was expressed by the temperature difference, and the test method was as follows: samples 1-8 were placed on a substrate and subjected to sunlight at an intensity of 1 kW / m². 2 The fabric was heated at a distance of 20cm for 10 minutes, and the surface temperature difference of samples 1-8 before and after heating was measured.

[0132] As can be seen from the test results in Table 1, the nylon fiber prepared by this invention has good aging resistance and mechanical properties, and also has light absorption and heat generation characteristics. This is because the modified nitrile rubber prepared in this invention contains an antioxidant component, and the TiN / carbon composite material has light absorption and heat generation properties. After the TiN / carbon composite material is surface modified with KH560, chemical bonds are formed through the reaction between epoxy groups and amino groups in the modified nitrile rubber, terminal hydroxyl groups and terminal carboxyl groups in PA6 under melt conditions. This not only improves the compatibility between the light absorption and heat generation additive, the modified nitrile rubber and PA6, but also improves the aging resistance and toughness of the light absorption and heat generation nylon fiber.

[0133] In Comparative Example 1, no antioxidant was added to the nitrile rubber, therefore the nitrile rubber did not have the two anti-aging structures of aromatic secondary amine and thiourea, so the anti-aging performance of Comparative Example 1 was not as good as that of the Example; in Comparative Example 2, the TiN / carbon composite material was not modified with KH560, which reduced the dispersion and compatibility of the light-absorbing and heat-generating inorganic material in the matrix, thus affecting the mechanical properties of the fiber; in Comparative Example 3, the light-absorbing and heat-generating additive did not contain TiN doping, and due to the synergistic effect of TiN material and carbon material in photothermal conversion performance, the light-absorbing and heat-generating performance of Comparative Example 3 was reduced.

[0134] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A method for producing a light-absorbing heat-generating nylon fiber, characterized by, The method comprises the following steps: Step (1), 4, 4'-diaminodiphenylamine, ethanol, dibutyltin dilaurate are mixed uniformly, and allyl isothiocyanate is added dropwise, and then the reaction is carried out; after the reaction is completed, the product is precipitated, filtered, washed and dried to obtain a reaction type antioxidant; Step (2), water, emulsifier, stabilizer and acrylonitrile are mixed, and then the reaction type antioxidant, butadiene, redox initiator, chelating agent and molecular weight regulator are added, and then the reaction is carried out; after the reaction is completed, the product is degassed and condensed, and then dried to obtain modified butyronitrile rubber; Step (3), TiN / carbon composite material, KH560 and isopropyl alcohol are mixed and stirred, and then filtered, washed and dried to obtain light-absorbing and heat-generating additive; The light-absorbing and heat-generating master batch is obtained by adding the light-absorbing and heat-generating additive and the modified butyronitrile rubber into PA6 chips in sequence, melt blending, extruding and cutting. The light-absorbing and heat-generating nylon fiber is obtained by blending the light-absorbing and heat-generating master batch with PA6 chips, melt spinning, cooling and drawing.

2. The method for preparing light-absorbing and heat-generating nylon fiber according to claim 1, characterized in that, In the step (1), the molar ratio of 4, 4'-diaminodiphenylamine to allyl isothiocyanate is 1:1-1.3; and the solid-liquid ratio of 4, 4'-diaminodiphenylamine, ethanol and dibutyltin dilaurate is 10g:60-100mL:0.05-0.08g.

3. The method for preparing light-absorbing and heat-generating nylon fiber according to claim 1, characterized in that, In the step (1), the reaction condition is that the reaction is carried out at 45-55℃ for 4-6h, and then the temperature is lowered to 20-25℃ for continuous reaction for 48h.

4. The method for preparing light-absorbing and heat-generating nylon fiber according to claim 1, characterized in that, In the step (2), the mass ratio of acrylonitrile, butadiene, water, emulsifier, stabilizer, reaction type antioxidant, redox initiator, chelating agent, molecular weight regulator is 20-30:70-80:200-300:5-5.5:0.005-0.006:2-3:0.2-0.3:0.03:0.4-0.5; the redox initiator, chelating agent and molecular weight regulator are added in a nitrogen atmosphere at 5-15℃; and the reaction condition is that the reaction is carried out at 5-30℃ for 7-12h.

5. The method for preparing light-absorbing and heat-generating nylon fiber according to claim 1, characterized in that, In the step (2), the emulsifier is prepared by mixing potassium abietate soap and sodium beta-naphthalenesulfonate formaldehyde condensate in a mass ratio of 10-15:1; and in the redox initiator, the mass ratio of dicumyl peroxide, ethylenediaminetetraacetic acid iron sodium salt, sodium formaldehyde sulfoxylate and sodium bisulfite is 8-10:0.5-1:8-10:2-3.

6. The method for preparing light-absorbing and heat-generating nylon fiber according to claim 1, characterized in that, In the step (3), the TiN / carbon composite material is prepared by the following steps: Wood sugar, acetic acid, TiN and water are mixed in a mass ratio of 25:15:1.5-2:400-600, and then the reaction is carried out at 190-220℃ for 3-7h; after the reaction is completed, the temperature is lowered to room temperature, the precipitate is obtained by filtration, washed with water and ethanol, and then dried to obtain the TiN / carbon composite material.

7. The method for preparing light-absorbing and heat-generating nylon fiber according to claim 1, characterized in that, In the step (3), the solid-liquid ratio of TiN / carbon composite material, KH560 and isopropyl alcohol is 10g:0.3-1g:300-400mL; and the reaction condition is that the stirring treatment is carried out at 55-65℃ for 1.5-3h.

8. The method for preparing light-absorbing and heat-generating nylon fiber according to claim 1, characterized in that, The mass ratio of the light-absorbing and heat-generating additive, the modified nitrile rubber and the PA6 chip in the step (3) is 1-2:10-20:80-90.

9. The method for preparing light-absorbing and heat-generating nylon fiber according to claim 1, characterized in that, The melt spinning condition in the step (3) is that the temperature is 270-280℃ in the first zone, 295-297℃ in the second zone, 290-292℃ in the third and fourth zones, the spinning speed is 800-1000m / min, and the draft ratio is 3-3.8 times. 10.A light-absorbing and heat-generating nylon fiber prepared by the preparation method of the light-absorbing and heat-generating nylon fiber according to any one of claims 1-9.

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