Corrosion-resistant antibacterial fiber and preparation method thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- NANTONG WORLD TEXTILE CO LTD
- Filing Date
- 2025-11-04
- Publication Date
- 2026-06-12
AI Technical Summary
Traditional polyimide fibers lack effective antibacterial properties and are prone to becoming carriers for bacterial attachment and reproduction in humid or microbial-rich environments, leading to fiber degradation and hygiene hazards. Furthermore, existing modification methods are prone to inactivation or dissolution in harsh chemical environments, making it difficult to meet the long-term requirements for both corrosion resistance and antibacterial properties during long-term use.
Corrosion-resistant and antibacterial fibers were prepared by introducing bisbenzimidazole diamine and phenylphosphamide dipropylene diamine structural units into the polyimide molecular chain and combining them with functionalized modified graphene oxide to form an amide bond crosslinking network.
It significantly improves the mechanical strength and thermal stability of the fiber, while providing a long-lasting and reliable antibacterial function, enhancing interfacial bonding and corrosion resistance, and achieving stable protection in harsh environments.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of functional fiber materials technology, specifically to a corrosion-resistant and antibacterial fiber and its preparation method. Background Technology
[0002] Polyimide fibers are a class of polymer materials with excellent thermal stability and mechanical properties. The rigid aromatic heterocyclic structure in their molecular backbone endows the material with outstanding high-temperature resistance, chemical corrosion resistance, and high mechanical strength, making them widely used in protective clothing, filter materials, and specialty industrial fabrics. However, traditional polyimide fibers themselves lack effective antibacterial functions. In humid or microbially enriched environments, they easily become carriers for bacterial attachment and reproduction, leading not only to fiber degradation and performance decline but also potential product contamination and hygiene hazards. Current methods of surface coating or blending with small-molecule antibacterial agents often suffer from uneven distribution of functional components, weak bonding with the matrix, and easy inactivation or dissolution in harsh chemical environments, making it difficult to meet the long-term requirements for both corrosion resistance and antibacterial properties during extended use.
[0003] With the increasing demand for high-performance protective materials in fields such as chemical engineering, environmental protection, and biomedicine, the development of fiber materials that combine excellent corrosion resistance and durable antibacterial properties has become a research focus. While traditional polyimide fibers possess good intrinsic chemical resistance, their functional modification capabilities are insufficient, limiting their further application in harsh corrosive and hygiene-sensitive environments. Therefore, introducing structural units with intrinsic antibacterial activity into the polymer molecular chain and further combining them with functionalized nanomaterials through composite spinning, while maintaining the fiber's original heat resistance and solvent resistance, to construct a stable and durable synergistic protective system of antibacterial and corrosion resistance, has become an important development direction for achieving technological innovation and application expansion in high-end protective fibers. Summary of the Invention
[0004] The purpose of this invention is to provide a corrosion-resistant and antibacterial fiber and its preparation method, so as to solve the problems existing in the prior art.
[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution:
[0006] A corrosion-resistant and antibacterial fiber, wherein the corrosion-resistant and antibacterial fiber is prepared by mixing a partially imidized polyimide spinning solution with a modified graphene oxide dispersion, followed by wet spinning and heat treatment.
[0007] As an optimization, the partially imidized polyimide spinning solution is prepared by reacting phenylphosphamide dipropylenediamine, bisbenzimidazole diamine, and 3,3',4,4'-biphenyltetracarboxylic anhydride.
[0008] As an optimization, the phenylphosphamide is prepared by reacting phenylphosphamide dichloride with 1,3-propanediamine.
[0009] As an optimization, the dibenzimidazole diamine is prepared by reacting oxalic acid, 4-nitro-1,2-phenylenediamine, ethylene glycol and polyphosphoric acid to obtain dinitrodibenzimidazole, followed by reduction.
[0010] As an optimization, the modified graphene oxide is prepared by reacting carboxylated graphene oxide with ethylenediamine and then with dicyandiamide.
[0011] A method for preparing a corrosion-resistant and antibacterial fiber includes the following preparation steps:
[0012] (1) Weigh phenylphosphine dichloride, 1,3-propanediamine and triethylamine in a mass ratio of 1:(1.0~1.2):(1.5~1.8); mix and dissolve 1,3-propanediamine, triethylamine and anhydrous tetrahydrofuran in a ratio of 1:(1.5~2):(3~4) to obtain a mixed solution; add phenylphosphine dichloride to anhydrous tetrahydrofuran at 10~20wt% in a nitrogen atmosphere, stir at 0~5℃ and 200~400r / min for 10~30min, add the mixed solution dropwise, raise the temperature to 25~30℃ and continue stirring. Stir for 4-6 hours, rotary evaporate, and wash with cold ether to obtain phenylphosphamide dipropylenediamine; mix oxalic acid, 4-nitro-1,2-phenylenediamine, ethylene glycol and polyphosphoric acid in a mass ratio of 1:(5-5.5):(80-90):(5-6), reflux and stir at 120-160℃ and 200-400 r / min for 8-12 hours, cool, filter, and wash to obtain dinitrobisbenzimidazole; weigh out two... Nitrobisbenzimidazole, palladium on carbon, 1,4-dioxane, hydrazine hydrate, and DMF; Nitrobisbenzimidazole, palladium on carbon, and 1,4-dioxane are mixed and stirred at 60-90℃ and 200-400 r / min for 10-20 min. Hydrazine hydrate is added and stirring continues for 6-10 h. DMF is added, and the temperature is raised to 90-110℃ and stirring continues for 10-30 min. The mixture is washed with water to obtain bisbenzimidazole diamine; it is prepared by mixing nitrobisbenzimidazole, palladium on carbon, 1,4-dioxane, hydrazine hydrate, and DMF in a mass ratio of 1:(0.35-0.7):(0.2-0.55):(8-9). Weigh 3,3',4,4'-biphenyltetracarboxylic anhydride, phenylphosphamide dipropylenediamine, bisbenzimidazole diamine and 1-methyl-2-pyrrolidone. Mix phenylphosphamide dipropylenediamine, bisbenzimidazole diamine and 1-methyl-2-pyrrolidone in a nitrogen atmosphere, stir at 0~5℃ and 50~150r / min for 20~40min, add 3,3',4,4'-biphenyltetracarboxylic anhydride and continue stirring for 24h, raise the temperature to 180~190℃ and continue stirring for 2h to obtain a partially imidized polyimide spinning solution;
[0013] (2) Weigh carboxylated graphene oxide, ethylenediamine, EDC and deionized water in a mass ratio of 1:(5~6):(2.5~3):(500~700); mix carboxylated graphene oxide, ethylenediamine and deionized water, sonicate for 5~10 min, add EDC, stir at 25~30℃ and 200~400 r / min for 10~14 h, centrifuge and wash to obtain aminated graphene oxide; weigh aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:(0.7~0.9):(800~1000), mix aminated graphene oxide and 0.1 mol / L hydrochloric acid, sonicate for 20~30 min, add dicyandiamide, stir at 90~100℃ and 200~400 r / min for 1.5~2.5 h, precipitate with ethanol, centrifuge and wash to obtain modified graphene oxide;
[0014] (3) Modified graphene oxide was added to 1-methyl-2-pyrrolidone and sonicated for 10-30 min to prepare a 4 mg / mL modified graphene oxide dispersion; a portion of imidized polyimide spinning solution was mixed with the modified graphene oxide dispersion at a volume ratio of 1:0.18-0.22, stirred at 25-30℃ and 200-400 r / min for 10-30 min, and after low-pressure room temperature degassing, it was transferred to the spinning barrel and wet-spun to prepare nascent fibers; the nascent fibers were placed in a high-temperature vacuum oven and treated at 150-200℃ for 0.5-1.5 h, and then subjected to hot stretching treatment at 300℃ to obtain corrosion-resistant and antibacterial fibers.
[0015] As an optimization, the palladium carbon in step (1) has a palladium content of 10% and is manufactured by Shanghai Yurui Chemical Co., Ltd.
[0016] As an optimization, the reaction process of partially imidizing polyimide in step (1) is as follows:
[0017]
[0018] As an optimization, the carboxylated graphene oxide sheets in step (2) have a diameter of 0.5~5μm and a thickness of 0.8~1.2nm, and are manufactured by Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.
[0019] As an optimization, the reaction process of the modified graphene oxide in step (2) is as follows:
[0020]
[0021] As an optimization, the wet spinning method in step (3) is as follows: a portion of the imidized polyimide and modified graphene oxide mixed spinning solution is extruded into a coagulation bath through a metering pump and a 50-hole × 80μm spinneret. The coagulation bath is a mixture of 1-methyl-2-pyrrolidone and deionized water in a volume ratio of 40:60, and the coagulation bath temperature is 25℃.
[0022] Compared with the prior art, the beneficial effects achieved by the present invention are:
[0023] In preparing corrosion-resistant and antibacterial fibers, this invention involves reacting phenylphosphamide dichloro, 1,3-propanediamine, and triethylamine to obtain phenylphosphamide dipropanediamine; reacting phenylphosphamide dipropanediamine, bisbenzimidazole diamine, and 3,3',4,4'-biphenyltetracarboxylic anhydride to obtain a partially imidized polyimide spinning solution; reacting carboxylated graphene oxide with ethylenediamine and then with dicyandiamide to obtain modified graphene oxide; mixing the partially imidized polyimide spinning solution with the modified graphene oxide dispersion, wet spinning to prepare nascent fibers, and then hot stretching treatment to obtain corrosion-resistant and antibacterial fibers.
[0024] First, by synergistically introducing rigid bisbenzimidazole diamine and phenylphosphamide dipropylene diamine structural units into the polyimide molecular backbone, not only is the rigid framework of the bisbenzimidazole ring enhanced, thereby significantly improving the mechanical strength and thermal stability of the fiber, but the introduction of the phenylphosphamide group also endows the material with excellent intrinsic flame retardancy. At the same time, through a partial imidization polymerization strategy, unreacted active groups such as carboxyl groups are retained on the polymer chain. These active groups provide reaction sites for subsequent chemical bonding with nanomaterials, which is the key to constructing a stable hierarchical structure.
[0025] Secondly, dicyandiamide was used to functionalize aminated graphene oxide, successfully introducing biguanide functional groups with efficient and broad-spectrum antibacterial properties onto the nanosheets. After this modified graphene oxide was blended with a partially imidized polyimide spinning solution, during the final heat treatment, the carboxyl groups retained on the matrix and the amino groups on the nanomaterial surface underwent further condensation reactions, forming a robust amide bond cross-linking network. This significantly enhances the interfacial bonding, enabling graphene oxide to effectively act as a physical barrier, thereby greatly improving the fiber's corrosion resistance. Furthermore, the biguanide functional groups are stably anchored within the fiber, achieving a dissolution-independent contact antibacterial mechanism, endowing the fiber with durable and reliable antibacterial function. Detailed Implementation
[0026] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0027] To more clearly illustrate the method provided by the present invention, the following embodiments will be described in detail. Example 1:
[0028] A method for preparing a corrosion-resistant and antibacterial fiber mainly includes the following preparation steps:
[0029] (1) Weigh phenylphosphamide dichloride, 1,3-propanediamine and triethylamine in a mass ratio of 1:1.0:1.5; mix 1,3-propanediamine, triethylamine and anhydrous tetrahydrofuran in a 1:1.5:3 ratio to obtain a mixed solution; add phenylphosphamide dichloride at 10 wt% to anhydrous tetrahydrofuran under a nitrogen atmosphere, stir at 0℃ and 200 r / min for 10 min, add the mixed solution dropwise, raise the temperature to 25℃ and continue stirring for 4 min. Benzylphosphamide was prepared by rotary evaporation and washing with cold ether. Oxalic acid, 4-nitro-1,2-phenylenediamine, ethylene glycol, and polyphosphoric acid were mixed in a mass ratio of 1:5:80:5 and refluxed at 120℃ and 200 r / min for 8 h. After cooling, filtration, and washing, dinitrobisbenzimidazole was prepared. Dinitrobisbenzimidazole, palladium on carbon, and 1,4-dioxane were weighed in a mass ratio of 1:0.08:8:1.5:2. 1,4-dioxane, hydrazine hydrate, and DMF were mixed; 1,4-dioxane, bis(benzimidazole), palladium on carbon, and 1,4-dioxane were stirred at 60°C and 200 rpm for 10 min; hydrazine hydrate was added and stirring continued for 6 h; DMF was added; the mixture was heated to 90°C and stirred for 10 min; the mixture was washed with water to obtain bis(benzimidazole)diamine; 3,3',4,4'-biphenyltetracarboxylic anhydride, benzene, and hydroxyl group were weighed according to a mass ratio of 1:0.35:0.55:8. Phenylphosphonyl dipropylenediamine, bisbenzimidazole diamine, and 1-methyl-2-pyrrolidone were mixed under a nitrogen atmosphere and stirred at 0°C and 50 r / min for 20 min. Then, 3,3',4,4'-biphenyltetracarboxylic anhydride was added and stirring was continued for 24 h. The mixture was then heated to 180°C and stirred for 2 h to obtain a partially imidized polyimide spinning solution.
[0030] (2) Weigh carboxylated graphene oxide, ethylenediamine, EDC and deionized water in a mass ratio of 1:5:2.5:500; mix carboxylated graphene oxide, ethylenediamine and deionized water, sonicate for 5 min, add EDC, stir at 25℃ and 200 r / min for 10 h, and centrifuge and wash to obtain aminated graphene oxide; weigh aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:0.8:800, mix aminated graphene oxide and 0.1 mol / L hydrochloric acid, sonicate for 20 min, add dicyandiamide, stir at 95℃ and 200 r / min for 2 h, precipitate with ethanol, and centrifuge and wash to obtain modified graphene oxide;
[0031] (3) Modified graphene oxide was added to 1-methyl-2-pyrrolidone and sonicated for 10 min to prepare a 4 mg / mL modified graphene oxide dispersion; a portion of imidized polyimide spinning solution was mixed with the modified graphene oxide dispersion at a volume ratio of 1:0.2, stirred at 25℃ and 200 r / min for 10 min, and after low-pressure room temperature degassing, it was transferred to the spinning barrel and wet-spun to prepare nascent fibers; the nascent fibers were placed in a high-temperature vacuum oven and treated at 150℃ for 0.5 h, and then subjected to hot stretching treatment at 300℃ to obtain corrosion-resistant and antibacterial fibers. Example 2:
[0032] A method for preparing a corrosion-resistant and antibacterial fiber mainly includes the following preparation steps:
[0033] (1) Weigh phenylphosphine dichloride, 1,3-propanediamine and triethylamine in a mass ratio of 1:1.1:1.7; mix 1,3-propanediamine, triethylamine and anhydrous tetrahydrofuran in a mass ratio of 1:1.8:3.5 to obtain a mixed solution; add phenylphosphine dichloride at 15wt% to anhydrous tetrahydrofuran in a nitrogen atmosphere, stir at 300r / min for 20min at 3℃, add the mixed solution dropwise, raise the temperature to 27℃ and continue stirring for 5h. Phenylated phosphoric acid dipropylenediamine was prepared by rotary evaporation and washing with cold ether. Oxalic acid, 4-nitro-1,2-phenylenediamine, ethylene glycol, and polyphosphoric acid were mixed in a mass ratio of 1:5.3:85:5.5 and refluxed at 140℃ and 300 r / min for 10 h. After cooling, filtration, and washing, dinitrobisbenzimidazole was prepared. Dinitrobisbenzimidazole, palladium on carbon, and 1,4-phenylenediamine were weighed in a mass ratio of 1:0.1:10:1.55:2.5. Dioxane, hydrazine hydrate, and DMF; dinitrobisbenzimidazole, palladium on carbon, and 1,4-dioxane were mixed and stirred at 80℃ and 300 rpm for 15 min. Hydrazine hydrate was added and stirring continued for 8 h. DMF was added, and the mixture was heated to 100℃ and stirred for 20 min. The mixture was washed with water to obtain bisbenzimidazole diamine; 3,3',4,4'-biphenyltetracarboxylic acid was weighed at a mass ratio of 1:0.55:0.35:8.5. 3,3',4,4'-biphenyltetracarboxylic anhydride, phenylphosphamide, bisbenzimidazole diamine and 1-methyl-2-pyrrolidone were mixed in a nitrogen atmosphere and stirred at 3°C and 100 r / min for 30 min. Then, 3,3',4,4'-biphenyltetracarboxylic anhydride was added and stirring was continued for 24 h. The temperature was raised to 185°C and stirring was continued for 2 h to obtain a partially imidized polyimide spinning solution.
[0034] (2) Weigh carboxylated graphene oxide, ethylenediamine, EDC and deionized water in a mass ratio of 1:5.5:2.8:600; mix carboxylated graphene oxide, ethylenediamine and deionized water, sonicate for 8 min, add EDC, stir at 27℃ and 300 r / min for 12 h, centrifuge and wash to obtain aminated graphene oxide; weigh aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:0.8:900, mix aminated graphene oxide and 0.1 mol / L hydrochloric acid, sonicate for 25 min, add dicyandiamide, stir at 95℃ and 300 r / min for 2 h, precipitate with ethanol, centrifuge and wash to obtain modified graphene oxide;
[0035] (3) Modified graphene oxide was added to 1-methyl-2-pyrrolidone and sonicated for 20 min to prepare a 4 mg / mL modified graphene oxide dispersion; a portion of imidized polyimide spinning solution was mixed with the modified graphene oxide dispersion at a volume ratio of 1:0.2, stirred at 27℃ and 300 r / min for 20 min, and after low-pressure room temperature degassing, it was transferred to the spinning barrel and wet-spun to prepare nascent fibers; the nascent fibers were placed in a high-temperature vacuum oven and treated at 180℃ for 1 h, and then subjected to hot stretching treatment at 300℃ to obtain corrosion-resistant and antibacterial fibers. Example 3:
[0036] A method for preparing a corrosion-resistant and antibacterial fiber includes the following preparation steps:
[0037] (1) Weigh phenylphosphine dichloride, 1,3-propanediamine and triethylamine in a mass ratio of 1:1.2:1.8; mix 1,3-propanediamine, triethylamine and anhydrous tetrahydrofuran in a 1:2:4 ratio to obtain a mixed solution; add phenylphosphine dichloride at 20 wt% to anhydrous tetrahydrofuran in a nitrogen atmosphere, stir at 5 °C and 400 r / min for 30 min, add the mixed solution dropwise, raise the temperature to 30 °C and continue stirring for 6 h. Phenylenol dipropylenediamine was prepared by rotary evaporation and washing with cold ether. Oxalic acid, 4-nitro-1,2-phenylenediamine, ethylene glycol, and polyphosphoric acid were mixed in a mass ratio of 1:5.5:90:6 and refluxed at 160℃ and 400 r / min for 12 h. After cooling, filtration, and washing, dinitrobisbenzimidazole was prepared. Dinitrobisbenzimidazole, palladium on carbon, and 1,4-dioxane were weighed in a mass ratio of 1:0.12:2:1.6:3. 1,4-dioxane, hydrazine hydrate, and DMF were mixed; dinitrobisbenzimidazole, palladium on carbon, and 1,4-dioxane were stirred at 90℃ and 400 r / min for 20 min, hydrazine hydrate was added and stirring was continued for 10 h, DMF was added, the temperature was raised to 110℃ and stirring was continued for 30 min, and the mixture was washed with water to obtain bisbenzimidazole diamine; 3,3',4,4'-biphenyltetracarboxylic anhydride, benzene, and hydroxyl group were weighed according to a mass ratio of 1:0.7:0.2:9. Phenylphosphonyl dipropylenediamine, bisbenzimidazole diamine and 1-methyl-2-pyrrolidone were mixed in a nitrogen atmosphere and stirred at 5°C and 150 r / min for 40 min. Then, 3,3',4,4'-biphenyltetracarboxylic anhydride was added and stirring was continued for 24 h. The temperature was raised to 190°C and stirring was continued for 2 h to obtain a partially imidized polyimide spinning solution.
[0038] (2) Weigh carboxylated graphene oxide, ethylenediamine, EDC and deionized water in a mass ratio of 1:6:3:700; mix carboxylated graphene oxide, ethylenediamine and deionized water, sonicate for 10 min, add EDC, stir at 30℃ and 400 r / min for 14 h, and centrifuge and wash to obtain aminated graphene oxide; weigh aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:0.8:1000, mix aminated graphene oxide and 0.1 mol / L hydrochloric acid, sonicate for 30 min, add dicyandiamide, stir at 95℃ and 300 r / min for 2 h, precipitate with ethanol, and centrifuge and wash to obtain modified graphene oxide;
[0039] (3) Modified graphene oxide was added to 1-methyl-2-pyrrolidone and sonicated for 30 min to prepare a 4 mg / mL modified graphene oxide dispersion; a portion of imidized polyimide spinning solution was mixed with the modified graphene oxide dispersion at a volume ratio of 1:0.2, stirred at 30℃ and 400 r / min for 30 min, and after low-pressure room temperature degassing, it was transferred to the spinning barrel and wet-spun to prepare nascent fibers; the nascent fibers were placed in a high-temperature vacuum oven and treated at 190℃ for 1.5 h, and then subjected to hot stretching treatment at 300℃ to obtain corrosion-resistant and antibacterial fibers. Example 4:
[0040] The only difference from Example 2 is step (2), which changes "weighing aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:0.8:1000" to "weighing aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:0.7:1000". Example 5:
[0041] The only difference from Example 2 is step (2), which changes "weighing aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:0.8:1000" to "weighing aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:0.9:1000". Example 6:
[0042] The only difference from Example 2 is the difference in step (2). In step (2), "Weigh out aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid at a mass ratio of 1:0.8:1000, mix aminated graphene oxide with 0.1 mol / L hydrochloric acid, sonicate for 30 min, add dicyandiamide, stir at 95°C and 300 r / min for 2 h, precipitate with ethanol, and centrifuge and wash to obtain modified graphene oxide", the "at 95°C" is changed to "at 90°C". Example 7:
[0043] The only difference from Example 2 is step (2), where “at 95°C” is changed to “at 100°C”.
[0044] Comparative Example 1:
[0045] The only difference from Example 2 is step (2), which changes "weighing aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:0.8:1000" to "weighing aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:0.6:1000".
[0046] Comparative Example 2:
[0047] The only difference from Example 2 is step (2), where “weigh out aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:0.8:1000” is changed to “weigh out aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:1:1000”.
[0048] Comparative Example 3:
[0049] The only difference from Example 2 is the difference in step (2). In step (2), "Weigh out aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid at a mass ratio of 1:0.8:1000, mix aminated graphene oxide with 0.1 mol / L hydrochloric acid, sonicate for 30 min, add dicyandiamide, stir at 95°C and 300 r / min for 2 h, precipitate with ethanol, and centrifuge and wash to obtain modified graphene oxide", the "at 95°C" is changed to "at 80°C".
[0050] Comparative Example 4:
[0051] The only difference from Example 2 is step (2), where “at 95°C” is changed to “at 110°C”.
[0052] Comparative Example 5:
[0053] The only difference from Example 2 is the difference in step (2). In step (2), "Weigh out aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid at a mass ratio of 1:0.8:1000, mix aminated graphene oxide with 0.1 mol / L hydrochloric acid, sonicate for 30 min, add dicyandiamide, stir at 95°C and 300 r / min for 2 h, precipitate with ethanol, and centrifuge and wash to obtain modified graphene oxide", the "stir at 300 r / min for 2 h" is changed to "stir at 300 r / min for 1 h".
[0054] Comparative Example 6:
[0055] The only difference from Example 2 is step (2), where “stirring at 300 r / min for 2 hours” is changed to “stirring at 300 r / min for 3 hours”.
[0056] Comparative Example 7:
[0057] The only difference from Example 2 is the step (3), where “mixing part of the imidized polyimide spinning solution with the modified graphene oxide dispersion at a volume ratio of 1:0.2” is changed to “mixing part of the imidized polyimide spinning solution with the modified graphene oxide dispersion at a volume ratio of 1:0.1”.
[0058] Comparative Example 8:
[0059] The only difference from Example 2 is the step (3), where “mixing part of the imidized polyimide spinning solution with the modified graphene oxide dispersion at a volume ratio of 1:0.2” is changed to “mixing part of the imidized polyimide spinning solution with the modified graphene oxide dispersion at a volume ratio of 1:0.15”.
[0060] Comparative Example 9:
[0061] The only difference from Example 2 is the step (3), where “mixing part of the imidized polyimide spinning solution with the modified graphene oxide dispersion at a volume ratio of 1:0.2” is changed to “mixing part of the imidized polyimide spinning solution with the modified graphene oxide dispersion at a volume ratio of 1:0.25”.
[0062] Comparative Example 10:
[0063] A method for preparing a corrosion-resistant and antibacterial fiber mainly includes the following preparation steps:
[0064] (1) Oxalic acid, 4-nitro-1,2-phenylenediamine, ethylene glycol and polyphosphoric acid were mixed in a mass ratio of 1:5.3:85:5.5 and refluxed at 140℃ and 300 r / min for 10 h. After cooling, filtration and washing, dinitrobisbenzimidazole was obtained. Dinitrobisbenzimidazole, palladium on carbon, 1,4-dioxane, hydrazine hydrate and DMF were weighed in a mass ratio of 1:0.1:10:1.55:2.5. Dinitrobisbenzimidazole, palladium on carbon and 1,4-dioxane were mixed and stirred at 80℃ and 300 r / min for 15 min. Hydrazine hydrate was added and stirring was continued for 8 min. h, add DMF, heat to 100℃ and continue stirring for 20 min, wash with water to obtain bisbenzimidazole diamine; weigh 3,3',4,4'-biphenyltetracarboxylic anhydride, bisbenzimidazole diamine and 1-methyl-2-pyrrolidone at a mass ratio of 1:0.9:8.5, mix bisbenzimidazole diamine and 1-methyl-2-pyrrolidone in a nitrogen atmosphere, stir at 3℃ and 100 r / min for 30 min, add 3,3',4,4'-biphenyltetracarboxylic anhydride and continue stirring for 24 h, heat to 185℃ and continue stirring for 2 h to obtain partially imidized polyimide spinning solution;
[0065] (2) Weigh carboxylated graphene oxide, ethylenediamine, EDC and deionized water in a mass ratio of 1:5.5:2.8:600; mix carboxylated graphene oxide, ethylenediamine and deionized water, sonicate for 8 min, add EDC, stir at 27℃ and 300 r / min for 12 h, centrifuge and wash to obtain aminated graphene oxide; weigh aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:0.8:900, mix aminated graphene oxide and 0.1 mol / L hydrochloric acid, sonicate for 25 min, add dicyandiamide, stir at 95℃ and 300 r / min for 2 h, precipitate with ethanol, centrifuge and wash to obtain modified graphene oxide;
[0066] (3) Modified graphene oxide was added to 1-methyl-2-pyrrolidone and sonicated for 20 min to prepare a 4 mg / mL modified graphene oxide dispersion; a portion of imidized polyimide spinning solution was mixed with the modified graphene oxide dispersion at a volume ratio of 1:0.2, stirred at 27℃ and 300 r / min for 20 min, and after low-pressure room temperature degassing, it was transferred to the spinning barrel and wet-spun to prepare nascent fibers; the nascent fibers were placed in a high-temperature vacuum oven and treated at 180℃ for 1 h, and then subjected to hot stretching treatment at 300℃ to obtain corrosion-resistant and antibacterial fibers.
[0067] Comparative Example 11:
[0068] A method for preparing a corrosion-resistant and antibacterial fiber mainly includes the following preparation steps:
[0069] (1) Phenylphosphoryl dichloride, 1,3-propanediamine and triethylamine were weighed in a mass ratio of 1:1.1:1.7; 1,3-propanediamine, triethylamine and anhydrous tetrahydrofuran were mixed and dissolved in a mass ratio of 1:1.8:3.5 to obtain a mixed solution; phenylphosphoryl dichloride was added to anhydrous tetrahydrofuran at 15 wt% under a nitrogen atmosphere, stirred at 300 r / min for 20 min at 3 °C, the mixed solution was added dropwise, the temperature was raised to 27 °C and stirring was continued for 5 h, rotary evaporated, and washed with cold diethyl ether to obtain phenylphosphoryl dipropanediamine. Amine; 3,3',4,4'-biphenyltetracarboxylic anhydride, phenylphosphamide dipropylenediamine and 1-methyl-2-pyrrolidone were weighed at a mass ratio of 1:0.92:8.5. Phenylphosphamide dipropylenediamine and 1-methyl-2-pyrrolidone were mixed in a nitrogen atmosphere and stirred at 3°C and 100 r / min for 30 min. 3,3',4,4'-biphenyltetracarboxylic anhydride was added and stirring was continued for 24 h. The temperature was raised to 185°C and stirring was continued for 2 h to obtain a partially imidized polyimide spinning solution.
[0070] (2) Weigh carboxylated graphene oxide, ethylenediamine, EDC and deionized water in a mass ratio of 1:5.5:2.8:600; mix carboxylated graphene oxide, ethylenediamine and deionized water, sonicate for 8 min, add EDC, stir at 27℃ and 300 r / min for 12 h, centrifuge and wash to obtain aminated graphene oxide; weigh aminated graphene oxide, dicyandiamide and 0.1 mol / L hydrochloric acid in a mass ratio of 1:0.8:900, mix aminated graphene oxide and 0.1 mol / L hydrochloric acid, sonicate for 25 min, add dicyandiamide, stir at 95℃ and 300 r / min for 2 h, precipitate with ethanol, centrifuge and wash to obtain modified graphene oxide;
[0071] (3) Modified graphene oxide was added to 1-methyl-2-pyrrolidone and sonicated for 20 min to prepare a 4 mg / mL modified graphene oxide dispersion; a portion of imidized polyimide spinning solution was mixed with the modified graphene oxide dispersion at a volume ratio of 1:0.2, stirred at 27℃ and 300 r / min for 20 min, and after low-pressure room temperature degassing, it was transferred to the spinning barrel and wet-spun to prepare nascent fibers; the nascent fibers were placed in a high-temperature vacuum oven and treated at 180℃ for 1 h, and then subjected to hot stretching treatment at 300℃ to obtain corrosion-resistant and antibacterial fibers.
[0072] Comparative Example 12:
[0073] A method for preparing a corrosion-resistant and antibacterial fiber mainly includes the following preparation steps:
[0074] (1) Weigh phenylphosphine dichloride, 1,3-propanediamine and triethylamine in a mass ratio of 1:1.1:1.7; mix 1,3-propanediamine, triethylamine and anhydrous tetrahydrofuran in a mass ratio of 1:1.8:3.5 to obtain a mixed solution; add phenylphosphine dichloride at 15wt% to anhydrous tetrahydrofuran in a nitrogen atmosphere, stir at 300r / min for 20min at 3℃, add the mixed solution dropwise, raise the temperature to 27℃ and continue stirring for 5h. Phenylenol-1,2-phenylenediamine was prepared by rotary evaporation and washing with cold ether. Oxalic acid, 4-nitro-1,2-phenylenediamine, ethylene glycol, and polyphosphoric acid were mixed in a mass ratio of 1:5.3:85:5.5 and refluxed at 140℃ and 300 r / min for 10 h. After cooling, filtration, and washing, dinitrobisbenzimidazole was prepared. Dinitrobisbenzimidazole, palladium on carbon, and 1,4-phenylenediamine were weighed in a mass ratio of 1:0.1:10:1.55:2.5. - Dioxane, hydrazine hydrate, and DMF; Dinitrobisbenzimidazole, palladium on carbon, and 1,4-dioxane were mixed and stirred at 80℃ and 300 r / min for 15 min. Hydrazine hydrate was added and stirring continued for 8 h. DMF was added, and the mixture was heated to 100℃ and stirred for 20 min. The mixture was washed with water to obtain bisbenzimidazole diamine; 3,3',4,4'-biphenyltetracarboxylic acid was weighed in a mass ratio of 1:0.5:0.45:8.5. 3,3',4,4'-biphenyltetracarboxylic anhydride, phenylphosphamide, bisbenzimidazole diamine and 1-methyl-2-pyrrolidone were mixed in a nitrogen atmosphere and stirred at 3°C and 100 r / min for 30 min. Then, 3,3',4,4'-biphenyltetracarboxylic anhydride was added and stirring was continued for 24 h. The temperature was raised to 185°C and stirring was continued for 2 h to obtain a partially imidized polyimide spinning solution.
[0075] (2) Weigh carboxylated graphene oxide, ethylenediamine, EDC and deionized water in a mass ratio of 1:5.5:2.8:600; mix carboxylated graphene oxide, ethylenediamine and deionized water, sonicate for 8 min, add EDC, stir at 27℃ and 300 r / min for 12 h, and centrifuge and wash to obtain aminated graphene oxide;
[0076] (3) Aminated graphene oxide was added to 1-methyl-2-pyrrolidone and sonicated for 20 min to prepare an aminated graphene oxide dispersion of 4 mg / mL; a portion of imidized polyimide spinning solution was mixed with the aminated graphene oxide dispersion at a volume ratio of 1:0.2, stirred at 27℃ and 300 r / min for 20 min, and after low-pressure room temperature degassing, it was transferred to the spinning barrel and wet-spun to prepare nascent fibers; the nascent fibers were placed in a high-temperature vacuum oven and treated at 180℃ for 1 h, and then subjected to hot stretching treatment at 300℃ to obtain corrosion-resistant and antibacterial fibers.
[0077] Comparative Example 13:
[0078] A method for preparing a corrosion-resistant and antibacterial fiber mainly includes the following preparation steps:
[0079] (1) Weigh phenylphosphine dichloride, 1,3-propanediamine and triethylamine in a mass ratio of 1:1.1:1.7; mix 1,3-propanediamine, triethylamine and anhydrous tetrahydrofuran in a mass ratio of 1:1.8:3.5 to obtain a mixed solution; add phenylphosphine dichloride at 15wt% to anhydrous tetrahydrofuran in a nitrogen atmosphere, stir at 300r / min for 20min at 3℃, add the mixed solution dropwise, raise the temperature to 27℃ and continue stirring for 5h. Phenylenol-1,2-phenylenediamine was prepared by rotary evaporation and washing with cold ether. Oxalic acid, 4-nitro-1,2-phenylenediamine, ethylene glycol, and polyphosphoric acid were mixed in a mass ratio of 1:5.3:85:5.5 and refluxed at 140℃ and 300 r / min for 10 h. After cooling, filtration, and washing, dinitrobisbenzimidazole was prepared. Dinitrobisbenzimidazole, palladium on carbon, and 1,4-phenylenediamine were weighed in a mass ratio of 1:0.1:10:1.55:2.5. - Dioxane, hydrazine hydrate, and DMF; Dinitrobisbenzimidazole, palladium on carbon, and 1,4-dioxane were mixed and stirred at 80℃ and 300 r / min for 15 min. Hydrazine hydrate was added and stirring continued for 8 h. DMF was added, and the mixture was heated to 100℃ and stirred for 20 min. The mixture was washed with water to obtain bisbenzimidazole diamine; 3,3',4,4'-biphenyltetracarboxylic acid was weighed in a mass ratio of 1:0.5:0.45:8.5. 3,3',4,4'-biphenyltetracarboxylic anhydride, phenylphosphamide, bisbenzimidazole diamine and 1-methyl-2-pyrrolidone were mixed in a nitrogen atmosphere and stirred at 3°C and 100 r / min for 30 min. Then, 3,3',4,4'-biphenyltetracarboxylic anhydride was added and stirring was continued for 24 h. The temperature was raised to 200°C and stirring was continued for 2 h to obtain a partially imidized polyimide spinning solution.
[0080] (2) After degassing at low pressure and room temperature, part of the imidized polyimide spinning solution is transferred to the spinning barrel and wet spinning is used to obtain corrosion-resistant and antibacterial fibers.
[0081] Experimental Example 1:
[0082] Optimal conditions for modified graphene oxide were determined (dicyandiamide addition amount, reaction temperature, and reaction time).
[0083] Test method: Antibacterial performance analysis. The antibacterial properties of the corrosion-resistant antibacterial fiber against Staphylococcus aureus and Escherichia coli were tested using the oscillation method according to the national standard GB / T20944.3-2008.
[0084] Antibacterial rate = [(Control sample viable bacteria concentration - Sample viable bacteria concentration) / Control sample viable bacteria concentration] × 100%
[0085] The results are shown in Table 1.
[0086] Table 1
[0087]
[0088] A comparison of Example 2 with Comparative Examples 1-2 and Examples 4-5 reveals that the amount of dicyandiamide has a significant impact on the antibacterial properties of the fibers. When the amount of dicyandiamide is small, the reaction with aminated graphene oxide is insufficient, resulting in fewer grafted antibacterial groups and thus lower antibacterial performance. Since dicyandiamide can undergo self-polymerization or form ineffective complexes under hydrochloric acid conditions, a higher concentration of dicyandiamide leads to more self-polymers. In this case, the self-polymerization reaction of dicyandiamide competes with the grafting reaction, reducing the effective antibacterial sites and resulting in lower antibacterial performance. Experiments show that the highest antibacterial performance is achieved when the amount of dicyandiamide is 0.8 times the mass of aminated graphene oxide.
[0089] A comparison of Examples 2 and Comparative Examples 3-4 and Examples 6-7 revealed that the highest antibacterial rate was achieved at a reaction temperature of 95°C. At lower reaction temperatures, insufficient molecular thermal kinetic energy resulted in a slow reaction rate, hindering the full grafting reaction between dicyandiamide and aminated graphene oxide. This led to a lower amount of effectively fixed antibacterial groups and consequently, lower antibacterial performance. Furthermore, because dicyandiamide is structurally unstable under high-temperature acidic conditions, excessively high reaction temperatures could cause some dicyandiamide to decompose or undergo side reactions, reducing its concentration for effective grafting. Experiments showed that the antibacterial performance was optimal when the reaction temperature was controlled at 95°C.
[0090] A comparison of Example 2 and Comparative Examples 5-6 reveals that when the reaction time is short, the grafting reaction between dicyandiamide and aminated graphene oxide is not fully completed, resulting in insufficient fixation of effective antibacterial groups and consequently lower antibacterial performance of the final fiber. Since this grafting reaction is carried out in an acidic aqueous medium, excessively long reaction times may lead to some degree of hydrolysis and chain breakage of the successfully grafted antibacterial chemical bonds. Furthermore, prolonged reaction times may induce other adverse side reactions in dicyandiamide molecules or their grafting products. Therefore, the antibacterial performance is optimal when the reaction time is controlled at 2 hours.
[0091] Experimental Example 2:
[0092] Determination of the optimal addition amount of modified graphene oxide
[0093] Test method: Determined by corrosion resistance. The samples were immersed in 0.01 mol / L hydrochloric acid solution and 0.01 mol / L sodium hydroxide solution for 10 h respectively. The fiber mass retention rate and tensile strength retention rate were tested before and after immersion. The tensile strength of the corrosion-resistant and antibacterial fiber was tested using a single fiber strength tester at a tensile speed of 10 mm / min.
[0094] Quality retention rate = [Material before soaking / Mass after soaking] × 100%
[0095] Tensile strength retention rate = [Tensile strength before immersion / Tensile strength after immersion] × 100%
[0096] The results are shown in Table 2.
[0097] Table 2
[0098]
[0099] A comparison of Examples 2 and Comparative Examples 7-9 reveals that the effect of modified graphene oxide on the corrosion resistance of the fibers initially increases and then decreases. This is because when the amount of modified graphene oxide added is appropriate, it can be uniformly dispersed in the polyimide matrix, effectively filling microscopic defects within the matrix and hindering the penetration path of corrosive media. Simultaneously, its excellent chemical inertness enhances the overall stability of the fiber, allowing it to better maintain its quality and strength in acidic and alkaline environments. However, when excessive amounts of modified graphene oxide are added, it easily agglomerates in the spinning solution, forming localized stress concentration points and creating defects within the fiber, weakening the overall integrity of the material and providing a preferential channel for the invasion of corrosive media. Therefore, a modified graphene oxide dispersion with a volume ratio of 0.2 yields the best overall corrosion resistance of the fibers.
[0100] Experimental Example 3:
[0101] Corrosion resistance, antibacterial properties, and flame retardant properties were tested.
[0102] Corrosion resistance test method: The corrosion-resistant and antibacterial fibers obtained in each example and the fibers of comparative examples 11-14 were immersed in 0.01 mol / L hydrochloric acid solution and 0.01 mol / L sodium hydroxide solution for 10 h, respectively, and the mass retention rate of the fibers before and after immersion was tested.
[0103] Quality retention rate = [Material before soaking / Mass after soaking] × 100%
[0104] Antibacterial performance test method: The corrosion-resistant antibacterial fibers obtained in each example and the fibers of comparative examples 11-14 were tested for antibacterial performance against Staphylococcus aureus and Escherichia coli using the oscillation method according to the national standard GB / T20944.3-2008.
[0105] Antibacterial rate = [(Control sample viable bacteria concentration - Sample viable bacteria concentration) / Control sample viable bacteria concentration] × 100%
[0106] Flame retardant performance test method: The corrosion-resistant and antibacterial fibers obtained in each example and the fibers of comparative examples 11 to 14 were tested according to the oxygen index method of FZ / T50017—2011 "Test method for flame retardant performance of polyester fibers".
[0107] The results are shown in Table 3.
[0108] Table 3
[0109]
[0110] A comparison of the experimental data from Examples 1-3 and Comparative Examples 10-13 in Table 3 reveals that the corrosion-resistant and antibacterial fibers prepared by this invention possess excellent corrosion resistance, antibacterial properties, and flame retardant properties.
[0111] By comparing Examples 1-3 and Comparative Example 10, it can be found that the introduction of phosphorus can effectively improve the flame retardant properties of fibers when polyimide is prepared by copolymerizing phenylphosphamide with 3,3',4,4'-biphenyltetracarboxylic anhydride and bisbenzimidazole diamine.
[0112] A comparison of Examples 1-3 and Comparative Example 11 reveals that the participation of the bisbenzimidazole diamine structural unit in copolymerization enhances the antibacterial properties of the final fiber. Bisbenzimidazole diamine, as a functional monomer, is chemically bonded to the polyimide backbone. Its benzimidazole ring system is a biologically active heterocyclic structure that can effectively interfere with the normal metabolic processes of microbial cells. It achieves a long-lasting, intrinsic antibacterial effect by inserting into microbial DNA molecules or inhibiting the activity of specific enzymes. This molecular-level dispersion achieved through copolymerization ensures the stable presence and long-term effectiveness of the antibacterial groups in the fiber.
[0113] By comparing Examples 1-3 and Comparative Example 12, it can be found that after dicyandiamide reacts under acidic conditions, it can introduce positively charged biguanide groups with highly efficient antibacterial activity onto the surface of graphene oxide. At the same time, this antibacterial group fixed by chemical bonds avoids the problems of easy migration and loss of small molecule antibacterial agents, giving the fiber a long-lasting and stable antibacterial effect.
[0114] A comparison of Examples 1-3 and Comparative Example 13 reveals that mixing modified graphene oxide with a portion of imidized polyimide spinning solution before spinning significantly enhances the antibacterial and corrosion-resistant properties of the final fiber. Regarding antibacterial properties, the dicyandiamide derivative guanidino functional groups grafted onto the surface of the modified graphene oxide provide highly efficient and long-lasting contact antibacterial activity. When uniformly dispersed in the polyimide matrix, they form numerous micro- and nano-scale antibacterial sites on the fiber surface. In terms of corrosion resistance, the nanosheet structure of the modified graphene oxide acts as an excellent physical barrier within the polyimide matrix, effectively extending the penetration path of corrosive media within the fiber. Furthermore, during heat treatment, the strong covalent bonding between the amino groups on the graphene oxide surface and the carboxyl groups of the imidized polyimide further enhances the fiber's density and reduces corrosion channels caused by interfacial defects, thereby significantly improving the fiber's chemical stability and mechanical property retention under acidic and alkaline conditions.
[0115] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.
Claims
1. A corrosion-resistant and antibacterial fiber, characterized in that, The corrosion-resistant and antibacterial fiber is prepared by mixing a partially imidized polyimide spinning solution with a modified graphene oxide dispersion, followed by wet spinning and heat treatment. The partially imidized polyimide spinning solution was prepared by reacting phenylphosphamide dipropylenediamine, bisbenzimidazole diamine and 3,3',4,4'-biphenyltetracarboxylic anhydride. The phenylphosphodipropanediamine is prepared by reacting phenylphosphodichloro and 1,3-propanediamine. The dibenzimidazole diamine is prepared by reacting oxalic acid, 4-nitro-1,2-phenylenediamine, ethylene glycol and polyphosphoric acid to obtain dinitrodibenzimidazole, followed by reduction. The modified graphene oxide is prepared by reacting carboxylated graphene oxide with ethylenediamine and then with dicyandiamide.
2. A method for preparing the corrosion-resistant and antibacterial fiber according to claim 1, characterized in that, The preparation steps include the following: (1) Phenylphosphoryl dichloro, 1,3-propanediamine, triethylamine and anhydrous tetrahydrofuran were weighed in a mass ratio of 1:(1.0~1.2):(1.5~1.8):(3~4), mixed and stirred at 25~30℃ to prepare phenylphosphoryl dipropanediamine; oxalic acid, 4-nitro-1,2-phenylenediamine, ethylene glycol and polyphosphoric acid were mixed in a mass ratio of 1:(5~5.5):(80~90):(5~6), and stirred at 120~160℃ to prepare dinitrobisbenzimidazole; and phenylphosphoryl dichloro, 1,3-propanediamine, triethylamine and anhydrous tetrahydrofuran were weighed in a mass ratio of 1:(1.0~1.2):(1.5~1.8):(3~4), mixed and stirred at 25~30℃ to prepare dinitrobisbenzimidazole; and dinitrobisbenzimidazole was prepared in a mass ratio of 1:(0.08~0.12):(8~12):(1 .5~1.6):(2~3) Weigh dinitrobisbenzimidazole, palladium on carbon, 1,4-dioxane, hydrazine hydrate and DMF, mix them and stir at 90~110℃ to prepare bisbenzimidazole diamine; Weigh 3,3',4,4'-biphenyltetracarboxylic anhydride, phenylphosphamide dipropylenediamine, bisbenzimidazole diamine and 1-methyl-2-pyrrolidone at a mass ratio of 1:(0.35~0.7):(0.2~0.55):(8~9), mix them and stir at 0~5℃, then heat to 180~190℃ to prepare partially imidized polyimide spinning solution; (2) Weigh carboxylated graphene oxide, ethylenediamine, EDC and deionized water in a mass ratio of 1:(5~6):(2.5~3):(500~700), mix and stir at 25~30℃ to prepare aminated graphene oxide; weigh aminated graphene oxide, dicyandiamide and hydrochloric acid in a mass ratio of 1:(0.7~0.9):(800~1000), mix and stir at 90~100℃ to prepare modified graphene oxide; (3) Mix a portion of imidized polyimide spinning solution with modified graphene oxide dispersion at a volume ratio of 1:0.18~0.22, degas at low pressure and room temperature, transfer to spinning barrel, and wet spin to prepare nascent fiber; place the nascent fiber in a high temperature vacuum oven and treat at 150~200℃, and then perform hot stretching treatment at 300℃ to obtain corrosion-resistant and antibacterial fiber.
3. The method for preparing a corrosion-resistant and antibacterial fiber according to claim 2, characterized in that, The palladium on carbon in step (1) has a palladium content of 10%.
4. The method for preparing a corrosion-resistant and antibacterial fiber according to claim 2, characterized in that, The carboxylated graphene oxide sheets in step (2) have a diameter of 0.5~5μm and a thickness of 0.8~1.2nm.
5. The method for preparing a corrosion-resistant and antibacterial fiber according to claim 2, characterized in that, The wet spinning method described in step (3) is as follows: a portion of the imidized polyimide and modified graphene oxide mixed spinning solution is extruded into a coagulation bath through a metering pump and a 50-hole × 80μm spinneret. The coagulation bath is a mixture of 1-methyl-2-pyrrolidone and deionized water in a volume ratio of 40:60, and the coagulation bath temperature is 25℃.