A bio-based nylon fiber with antistatic function and a preparation method thereof
By introducing polyethylene glycol into the copolymerization stage of bio-based nylon fibers, chemical bonds are formed and embedded into the nylon molecular chain, solving the problems of poor water resistance and dependence on petroleum-based products. This results in bio-based nylon fibers with permanent antistatic properties and good mechanical properties, suitable for industrial production and environmentally friendly applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANJING NANLI NEW MATERIALS CO LTD
- Filing Date
- 2026-05-06
- Publication Date
- 2026-06-30
AI Technical Summary
Existing antistatic nylon fibers have poor antistatic properties but are not resistant to washing, their mechanical properties deteriorate, and they rely on petroleum-based raw materials, making it difficult to meet the requirements of environmental protection and sustainable development.
Using bio-based 1,5-pentanediamine and bio-based dicarboxylic acid as raw materials, polyethylene glycol is introduced through a copolymerization stage to form chemical bonds embedded in the nylon molecular backbone, thus preparing bio-based nylon fibers with permanent antistatic function.
It achieves a good balance between the durability of antistatic effect and mechanical properties. The material is environmentally friendly and easy to industrialize, which meets the requirements of green development.
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Figure SMS_1
Abstract
Description
Technical Field
[0001] This invention belongs to the field of bio-based nylon fiber technology, and particularly relates to a bio-based nylon fiber with antistatic function and its preparation method. Background Technology
[0002] Nylon (polyamide fiber) is a synthetic fiber widely used in textiles, clothing, bags, and other fields due to its high strength and abrasion resistance. However, ordinary nylon fabrics do not possess antistatic properties and have high surface resistance, making them prone to static electricity buildup during use, attracting dust and affecting wearing comfort and appearance. Therefore, nylon fibers are required to have high antistatic properties to meet the performance requirements during use.
[0003] There are three main traditional methods for imparting antistatic properties to nylon fibers: surface finishing, blending modification, and copolymerization modification. For example, CN1958891A discloses an antistatic nylon fiber and its preparation method, which involves mixing a polymeric antistatic agent, polyamide, and processing aids in a mixer, followed by melt spinning in a twin-screw extruder to obtain nylon fibers with strong antistatic properties. CN20099663A discloses a method for preparing low-melting-point antistatic nylon fibers. This method uses an antistatic dispersion to randomly copolymerize with raw materials to prepare antistatic nylon fibers, wherein the antistatic dispersion is made of nano-antimony-doped tin dioxide. This nylon fiber has the characteristics of low melting point and high antistatic properties.
[0004] Most existing methods for preparing antistatic fibers primarily use petroleum-based nylons, such as nylon 6 or nylon 66, which does not meet current environmental and sustainable development requirements. Furthermore, fibers produced through antistatic agent post-treatment or blending processes are prone to antistatic agent detachment after repeated washing, making it difficult to achieve long-lasting antistatic properties. Therefore, there is a need to develop a bio-based nylon fiber with durable antistatic effects and excellent overall performance. Summary of the Invention
[0005] Objective: To overcome the shortcomings of existing antistatic nylon fibers, such as poor water resistance, decreased mechanical properties, and reliance on petroleum-based raw materials, this invention provides a bio-based nylon fiber with antistatic properties and its preparation method. This method uses bio-based 1,5-pentanediamine, bio-based diacid, and polyethylene glycol as raw materials. The reaction is carried out in the copolymerization stage, followed by pelleting, drying, and melt spinning to prepare bio-based nylon fibers with permanent antistatic properties. The introduced hydrophilic polyethylene glycol forms ion transport channels in the nylon matrix and endows the nylon fiber with antistatic properties. The resulting modified nylon fiber can be applied in functional textiles, conductive materials, and antistatic materials.
[0006] Technical solution: To achieve the above-mentioned objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides a method for preparing bio-based nylon fibers with antistatic function, comprising the following steps: S1: Under the protection of inert gas, bio-based 1,5-pentanediamine and dicarboxylic acid are added to deionized water in a certain proportion and stirred to form a uniform nylon salt solution. S2: The nylon salt solution, catalyst, and antioxidant are added to the polymerization reactor and heated to 200-230 °C under an inert gas atmosphere for polymerization reaction; then the temperature is raised to 240-260 °C, polyethylene glycol is added, vacuum is applied, and the reaction is carried out for 1-2 h; after the reaction is completed, inert gas is introduced, the material is discharged, cooled, stretched, pelletized, and dried to obtain modified bio-based nylon resin particles; S3: The modified bio-based nylon resin particles are melt-spun to obtain the bio-based nylon fiber with antistatic function.
[0007] As a specific implementation scheme, in step S1, the inert gas is one of nitrogen, helium, argon or carbon dioxide; preferably nitrogen; the dicarboxylic acid is selected from at least one of succinic acid, adipic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid and eicosanoic acid; As a specific implementation scheme, in step S1, the molar ratio of 1,5-pentanediamine to dicarboxylic acid is (1.01-1.05):1.
[0008] As a specific implementation scheme, in step S1, the solid content of the nylon salt solution is 60%-80%. After diluting 20 mL of the nylon salt solution to a concentration of 10%, its pH value is measured to be 7.7-8.0 at 25 °C.
[0009] As a specific implementation scheme, in step S2, the catalyst is one or more of hypophosphite, sodium hypophosphite, phosphoric acid, phosphorous acid and tetrabutyl titanate, and its addition amount is 100-300 ppm of the total mass of the nylon salt solution; The antioxidant is one of antioxidant 1098, antioxidant 1010, antioxidant 245, antioxidant 168 and antioxidant 626, and its addition amount is 50-100 ppm of the total mass of the nylon salt solution.
[0010] As a specific implementation scheme, in step S2, the polymerization reaction is carried out under a pressure maintained at 1.2-1.5 MPa for 2-3 hours.
[0011] As a specific implementation scheme, in step S2, the molecular weight of the polyethylene glycol is 500-3000, and its addition amount is 6%-12% of the total mass of the nylon salt solution.
[0012] As a specific implementation scheme, in step S2, the pelletizing is carried out using a pelletizer, the rotation speed of the pelletizer roller is 400-700 rpm, and the pelletizing time is 0.5-1.5 h; the drying temperature is 80-120 ℃, and the drying time is 4-6 h.
[0013] As a specific implementation scheme, in step S3, the melt spinning is carried out using a melt spinning machine, under the following conditions: the temperature of the spinning box is 240-260 ℃; the temperature of the spinneret is 220-270 ℃; cooling is performed by side blowing, with the side blowing temperature being 15-32 ℃, the air humidity being 30.0%-70.0%, and the air velocity being 0.2-1.5 m / s; and the winding speed being 800-1500 m / min.
[0014] Secondly, the present invention provides a bio-based nylon fiber with antistatic function, wherein the bio-based nylon fiber is mainly prepared by the above-mentioned preparation method.
[0015] The key innovations of this invention are as follows: 1. Adding polyethylene glycol during the copolymerization stage: Polyethylene glycol is added to the copolymerization reaction of bio-based nylon, allowing it to be embedded into the main chain of nylon molecules through chemical bonds, resulting in bio-based nylon fibers with permanent antistatic properties.
[0016] 2. Permanent antistatic mechanism: Polyethylene glycol segments endow the material with intrinsic antistatic properties. The antistatic effect is water-resistant and does not migrate, which is different from surface finishing and blending modification methods.
[0017] 3. Bio-based raw material system: Nylon salt solution is prepared using bio-based dicarboxylic acid and bio-based 1,5-pentanediamine, which replaces petroleum-based raw materials and is low-carbon and environmentally friendly.
[0018] Beneficial effects: Compared with the prior art, the present invention has the following advantages: (1) Long-lasting antistatic effect: Polyethylene glycol segments are embedded in the nylon molecular chain through chemical bonds to obtain modified polyethylene glycol nylon fibers, which have permanent antistatic properties.
[0019] (2) Good spinnability: The introduction of polyethylene glycol has little effect on the polymerization process. The resulting nylon resin has a uniform molecular weight distribution, good thermal stability, stable melt spinning process, low breakage rate, and is suitable for industrial production.
[0020] (3) Good environmental performance: Bio-based dicarboxylic acid and bio-based 1,5-pentanediamine are used as raw materials, which reduces the dependence on petroleum resources and reduces carbon emissions; polyethylene glycol itself is non-toxic and biodegradable, and the overall material conforms to the development direction of green and environmental protection.
[0021] (4) Simple and controllable process: This invention can be implemented directly on existing nylon polymerization equipment without the need for additional special equipment. The process conditions are similar to those of conventional nylon polymerization, making it easy to promote industrialization. Detailed Implementation
[0022] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. Example
[0023] A method for preparing bio-based nylon 56 fiber with antistatic function includes the following steps: Preparation of nylon salt solution: Under normal pressure and nitrogen protection, bio-based 1,5-pentanediamine and deionized water were mixed evenly, and adipic acid was slowly added until it was completely dissolved to prepare a clear and transparent nylon 56 salt solution. The molar ratio of 1,5-pentanediamine to adipic acid was 1.05:1, and the pH value at 25 °C was 7.7 (measured after diluting 20 mL of nylon salt solution to a 10% concentration). A nylon 56 salt solution with a solid content of 70 wt.% was obtained.
[0024] Preparation of antistatic bio-based nylon chips: A certain amount of the above-mentioned nylon salt solution, catalyst, and antioxidant were added to a polymerization reactor. The reactor was heated to 210 °C under a nitrogen atmosphere, with the pressure maintained at 1.3 MPa, and the polymerization reaction was carried out for 3 h. The temperature was then raised to 260 °C, and 6% (by mass) of polyethylene glycol (molecular weight 2000, added in solution form) of the total nylon salt solution was added. The pressure was slowly evacuated to -0.09 MPa, and polycondensation was carried out for 2 h. Afterward, inert gas was introduced into the reactor to an appropriate pressure, and the molten resin was cooled in a water bath, stretched, and granulated to obtain modified antistatic bio-based nylon resin chips. The catalyst was sodium hypophosphite, added at 150 ppm of the total nylon salt solution mass; the antioxidant was antioxidant 1010, added at 60 ppm of the total nylon salt solution mass.
[0025] The pelletizing process was carried out using a pelletizer with a roller speed of 500 rpm, a pelletizing time of 40 min, a particle drying temperature of 100℃, and a drying time of 6 h.
[0026] Preparation of antistatic bio-based nylon fibers: The dried chips were melt-spun using a melt spinning machine to obtain antistatic bio-based nylon fibers. The spinning temperature was set to 250 ℃, the spinneret temperature was 250 ℃, cooling was achieved by side blowing with a wind speed of 0.4 m / s, and the winding speed was 1200 m / min. Example
[0027] A method for preparing bio-based nylon 56 fiber with antistatic function includes the following steps: Preparation of nylon salt solution: Under normal pressure and nitrogen protection, bio-based 1,5-pentanediamine and deionized water were mixed evenly, and adipic acid was slowly added until it was completely dissolved to prepare a clear and transparent nylon 56 salt solution. The molar ratio of 1,5-pentanediamine to adipic acid was 1.05:1, and the pH value at 25 °C was 7.7 (measured after diluting 20 mL of nylon salt solution to a 10% concentration). A nylon 56 salt solution with a solid content of 70 wt.% was obtained.
[0028] Preparation of antistatic bio-based nylon chips: A certain amount of the above-mentioned nylon salt solution, catalyst, and antioxidant were added to a polymerization reactor. The reactor was heated to 220 °C under a nitrogen atmosphere, with the pressure maintained at 1.5 MPa, and the polymerization reaction was carried out for 3 h. The temperature was then raised to 260 °C, and 12% (by mass) of polyethylene glycol (molecular weight 2000, added in solution form) of the total nylon salt solution was added. The pressure was slowly evacuated to -0.09 MPa, and polycondensation was carried out for 2 h. Afterward, inert gas was introduced into the reactor to an appropriate pressure, and the molten resin was cooled in a water bath, stretched, and granulated to obtain modified antistatic bio-based nylon resin chips. The catalyst was sodium hypophosphite, added at 150 ppm of the total nylon salt solution mass; the antioxidant was antioxidant 1010, added at 60 ppm of the total nylon salt solution mass.
[0029] The pelletizing process was carried out using a pelletizer with a roller speed of 500 rpm, a pelletizing time of 40 min, a particle drying temperature of 100℃, and a drying time of 6 h.
[0030] Preparation of antistatic bio-based nylon fibers: The dried chips were melt-spun using a melt spinning machine to obtain antistatic bio-based nylon fibers. The spinning temperature was set to 250 ℃, the spinneret temperature was 250 ℃, cooling was achieved by side blowing with a wind speed of 0.4 m / s, and the winding speed was 1200 m / min. Example
[0031] A method for preparing bio-based nylon 56 fiber with antistatic function includes the following steps: Preparation of nylon salt solution: Under normal pressure and nitrogen protection, bio-based 1,5-pentanediamine and deionized water were mixed evenly, and adipic acid was slowly added until it was completely dissolved to prepare a clear and transparent nylon 56 salt solution. The molar ratio of 1,5-pentanediamine to adipic acid was 1.05:1, and the pH value at 25 °C was 7.7 (measured after diluting 20 mL of nylon salt solution to a 10% concentration). A nylon 56 salt solution with a solid content of 70 wt.% was obtained.
[0032] Preparation of antistatic bio-based nylon chips: A certain amount of the above-mentioned nylon salt solution, catalyst, and antioxidant were added to a polymerization reactor. The reactor was heated to 220 °C under a nitrogen atmosphere, with the pressure maintained at 1.5 MPa, and the polymerization reaction was carried out for 3 h. The temperature was then raised to 260 °C, and 6% (by mass) of polyethylene glycol (molecular weight 1000, added in solution form) of the total nylon salt solution was added. The pressure was slowly evacuated to -0.09 MPa, and polycondensation was carried out for 2 h. Afterward, inert gas was introduced into the reactor to an appropriate pressure, and the molten resin was cooled in a water bath, stretched, and granulated to obtain modified antistatic bio-based nylon resin chips. The catalyst was sodium hypophosphite, added at 150 ppm of the total nylon salt solution mass; the antioxidant was antioxidant 1010, added at 60 ppm of the total nylon salt solution mass.
[0033] The pelletizing process was carried out using a pelletizer with a roller speed of 500 rpm, a pelletizing time of 40 min, a particle drying temperature of 100℃, and a drying time of 6 h.
[0034] Preparation of antistatic bio-based nylon fibers: The dried chips were melt-spun using a melt spinning machine to obtain antistatic bio-based nylon fibers. The spinning temperature was set to 250 ℃, the spinneret temperature was 250 ℃, cooling was achieved by side blowing with a wind speed of 0.4 m / s, and the winding speed was 1200 m / min.
[0035] Comparative Example 1 Compared with Example 1, Comparative Example 1 did not add polyethylene glycol and prepared conventional bio-based nylon fibers, including the following steps: Preparation of nylon salt solution: Same as in Example 1.
[0036] Preparation of bio-based nylon chips: A certain amount of nylon salt solution, catalyst, and antioxidant were added to a polymerization reactor. The reactor was heated to 210 °C under a nitrogen atmosphere, with the pressure maintained at 1.3 MPa, and the polymerization reaction was carried out for 3 h. The temperature was then raised to 260 °C, and a vacuum was applied for another 2 h. After the reaction, inert gas was introduced into the reactor to an appropriate pressure. The molten resin was then cooled in a water bath, stretched, and pelletized to obtain bio-based nylon resin chips. The catalyst was sodium hypophosphite, added at 150 ppm of the total mass of the nylon salt solution; the antioxidant was antioxidant 1010, added at 60 ppm of the total mass of the nylon salt solution.
[0037] The pelletizing process was carried out using a pelletizer with a roller speed of 500 rpm, a pelletizing time of 40 min, a particle drying temperature of 100℃, and a drying time of 6 h.
[0038] Preparation of bio-based nylon fibers: Same as in Example 1.
[0039] Comparative Example 2 Compared with Example 1, Comparative Example 2 uses a blending modification method to add polyethylene glycol, including the following steps: Preparation of nylon salt solution and preparation of bio-based nylon slices: Same as Comparative Example 1.
[0040] Preparation of modified nylon chips: Dried nylon chips were mixed uniformly with 15% by mass of polyethylene glycol (molecular weight 2000, added in solution form), melt-blended using a twin-screw extruder, cooled, and pelletized to obtain blended modified nylon chips. The screw extruder was set with the following temperatures: Zone 1: 200 ℃; Zone 2: 230 ℃; Zone 3: 240 ℃.
[0041] Preparation of bio-based nylon fibers: Same as in Example 1.
[0042] Performance testing methods The tensile properties were tested according to the methods published in GB / T 14344-2022 Standard for Testing Tensile Properties of Chemical Fiber Filaments. The tensile property test items were breaking strength and elongation at break. The surface resistivity was tested according to the method published in GB / T 1410-2006 "Test Methods for Volume Resistivity and Surface Resistivity of Solid Insulating Materials". The resistivity test items were volume resistivity and surface resistivity.
[0043] Test Case Performance Testing The fibers prepared in the above embodiments and comparative examples were tested according to the above test standards, and the results are shown in Table 1.
[0044]
[0045] Table 1 shows that adding polyethylene glycol to copolymerize with bio-based nylon salt during the copolymerization stage can successfully prepare bio-based nylon fibers with antistatic properties, and the molecular weight and amount of polyethylene glycol added have a significant impact on the fiber properties. Furthermore, the results of Comparative Example 1 show that conventional bio-based nylon fibers without added polyethylene glycol do not possess antistatic properties.
[0046] In summary, this invention achieves a good balance between antistatic effect and fiber mechanical properties by copolymerizing polyethylene glycol with bio-based nylon salt solution during the copolymerization stage, allowing polyethylene glycol segments to be embedded into the nylon molecular backbone through chemical bonds, thus obtaining bio-based nylon antistatic fibers with excellent comprehensive performance.
[0047] The antistatic bio-based nylon fiber described in this patent has wide applications in multiple fields. In known applications, this fiber can be used in antistatic clothing, antistatic carpets, home textiles, and packaging materials for electronic components, exhibiting permanent antistatic properties, washability, and excellent mechanical properties. In potential applications, this fiber can be extended to automotive interiors, medical textiles, and as a reinforcing fiber for antistatic coatings. These applications cover both civilian and industrial uses, fully leveraging its intrinsically permanent antistatic properties, bio-based environmental friendliness, and excellent overall performance.
[0048] The embodiments of the present invention have been described in detail above with reference to specific examples. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.
Claims
1. A method for preparing bio-based nylon fiber with antistatic function, characterized in that, Includes the following steps: S1: Under the protection of inert gas, bio-based 1,5-pentanediamine and dicarboxylic acid are added to deionized water in a certain proportion and stirred to form a uniform nylon salt solution. S2: The nylon salt solution, catalyst, and antioxidant are added to the polymerization reactor and heated to 200-230 °C under an inert gas atmosphere for polymerization reaction; then the temperature is raised to 240-260 °C, polyethylene glycol is added, vacuum is applied, and the reaction is carried out for 1-2 hours; after the reaction is completed, inert gas is introduced, the material is discharged, cooled, stretched, pelletized, and dried to obtain modified bio-based nylon resin particles; S3: The modified bio-based nylon resin particles are melt-spun to obtain the bio-based nylon fiber with antistatic function.
2. The method for preparing bio-based nylon fiber with antistatic function according to claim 1, characterized in that, In step S1, the inert gas is one of nitrogen, helium, argon or carbon dioxide; preferably nitrogen; the dicarboxylic acid is selected from at least one of succinic acid, adipic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid and eicosanoic acid.
3. The method for preparing bio-based nylon fiber with antistatic function according to claim 1, characterized in that, In step S1, the molar ratio of 1,5-pentanediamine to dicarboxylic acid is (1.01-1.05):
1.
4. The method for preparing bio-based nylon fiber with antistatic function according to claim 1, characterized in that, In step S1, the solid content of the nylon salt solution is 60%-80%. After diluting 20 mL of the nylon salt solution to a concentration of 10%, its pH value is measured to be 7.7-8.0 at 25 °C.
5. The method for preparing bio-based nylon fiber with antistatic function according to claim 1, characterized in that, In step S2, the catalyst is one or more of hypophosphite, sodium hypophosphite, phosphoric acid, phosphorous acid, and tetrabutyl titanate, and its addition amount is 100-300 ppm of the total mass of the nylon salt solution. The antioxidant is one of antioxidant 1098, antioxidant 1010, antioxidant 245, antioxidant 168 and antioxidant 626, and its addition amount is 50-100 ppm of the total mass of the nylon salt solution.
6. The method for preparing bio-based nylon fiber with antistatic function according to claim 1, characterized in that, In step S2, the polymerization reaction is carried out under a pressure maintained at 1.2-1.5 MPa for 2-3 hours.
7. The method for preparing bio-based nylon fiber with antistatic function according to claim 1, characterized in that, In step S2, the polyethylene glycol has a molecular weight of 500-3000 and is added at 6%-12% of the total mass of the nylon salt solution.
8. The method for preparing bio-based nylon fiber with antistatic function according to claim 1, characterized in that, In step S2, the pelletizing is performed using a pelletizer with a roller speed of 400-700 rpm and a pelletizing time of 0.5-1.5 h; the drying temperature is 80-120 ℃ and the drying time is 4-6 h.
9. The method for preparing bio-based nylon fiber with antistatic function according to claim 1, characterized in that, In step S3, the melt spinning is carried out using a melt spinning machine under the following conditions: the temperature of the spinning box is 240-260 ℃; the temperature of the spinneret is 220-270 ℃; cooling is achieved by side blowing, with the side blowing temperature being 15-32 ℃, the air humidity being 30.0%-70.0%, and the air velocity being 0.2-1.5 m / s; and the winding speed being 800-1500 m / min.
10. A bio-based nylon fiber with antistatic function, characterized in that, The bio-based nylon fiber is mainly prepared by the preparation method described in any one of claims 1-9.