A deep-dyeable conductive fiber material and a method for preparing the same

Abstract

The application discloses a deep-dyeable conductive fiber material and a preparation method thereof. The method comprises the following steps: mixing polyester chips after drying with modified fillers and conductive additives, preparing master batches through double-screw melt extrusion, then performing high-temperature spinning melt extrusion, cooling and solidifying through circular blowing, performing three-step heat drawing, finally performing oiling, network processing, and winding into a silk cake to obtain the deep-dyeable conductive fiber material. The application has the beneficial effects that the mechanical properties and dyeing properties of the fiber are significantly improved by introducing the modified fillers, and the deep dyeing effect is further optimized by adding amphoteric monomers to enhance the dye adsorption sites and interface interaction.

Description

Technical Field

[0001] This invention belongs to the field of chemical fiber technology, specifically, it relates to a deep-dyeable conductive fiber material and its preparation method. Background Technology

[0002] Currently, conductive fiber materials are widely used in fields such as smart textiles, antistatic clothing, and electromagnetic shielding, but their development still faces many technical bottlenecks.

[0003] Traditional conductive fibers typically achieve conductivity by directly adding conductive fillers (such as carbon black and metal oxides) to the polymer matrix. However, this method often leads to uneven filler dispersion, affecting the fiber's mechanical properties and processing stability. Furthermore, conventional conductive fibers exhibit poor dyeing properties, making it difficult to achieve deep dyeing effects, thus limiting their application in functional textiles with high color requirements. Existing technologies have attempted to improve fiber dyeing properties through surface modification or the introduction of polar groups, but these methods often fail to balance conductivity and colorfastness, and the modification processes are complex and costly. Simultaneously, the insufficient compatibility between inorganic fillers and organic polymer matrices can easily lead to interfacial defects, reducing fiber strength and durability.

[0004] Therefore, developing a fiber material that combines excellent electrical conductivity, high mechanical strength, and deep dyeing properties has become an urgent problem to be solved in the field of chemical fiber technology. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a conductive fiber material that can be deeply dyed and its preparation method.

[0006] The objective of this invention can be achieved through the following technical solutions: A method for preparing a deep-dyeable conductive fiber material includes the following steps: mixing dried polyester chips with modified fillers and conductive additives, producing masterbatch by twin-screw melt extrusion, followed by high-temperature spinning melt extrusion, cooling and solidification by ring blowing, performing three-step hot stretching, and finally oiling, network treatment, and winding into a yarn cake to obtain the deep-dyeable conductive fiber material.

[0007] Ideally, the mass ratio of the polyester chips, modified filler, and conductive additive is 85-95:5-6:2-3.

[0008] In a more optimized manner, the preparation process of the modified filler is as follows: Step 1: Mix tetraethoxysilane, anhydrous ethanol, deionized water and ammonia, and stir magnetically at 30°C for 3-4 hours. Then add an ethanol solution of vinyltrimethoxysilane dropwise and continue the reaction at the same temperature for 24 hours. After the reaction is complete, separate the product by centrifugation, wash and dry to obtain vinyl-functionalized nano silica. Step 2: Add glycidyl methacrylate, maleic anhydride and amphoteric monomer to N,N-dimethylformamide, adjust the pH to 5, add vinyl-functionalized nano-silica, stir evenly, add ammonium persulfate solution dropwise under a protective atmosphere, raise the temperature to 85-90℃, react for 3-4 hours, after the reaction is completed, perform post-treatment to obtain the modified filler.

[0009] In a more optimized manner, the raw materials for preparing the vinyl functionalized nano silica include the following components: by weight, 10-12 parts of tetraethoxysilane, 80-100 parts of anhydrous ethanol, 10-15 parts of deionized water, 2-5 parts of ammonia, and 5-10 parts of an ethanol solution of vinyltrimethoxysilane; wherein the concentration of the ethanol solution of vinyltrimethoxysilane is 20 wt%.

[0010] In a more optimized manner, the raw materials for preparing the modified filler include the following components: by weight, 20-30 parts glycidyl methacrylate, 5-10 parts maleic anhydride, 5-15 parts amphoteric monomer, 100-150 parts N,N-dimethylformamide, 10-20 parts vinyl-functionalized nano-silica, and 1-3 parts ammonium persulfate solution; wherein the concentration of the ammonium persulfate solution is 5 wt%.

[0011] In a more optimized manner, the preparation process of the amphoteric monomer is as follows: S1: Under a protective atmosphere, 4-vinylbenzyl chloride was dissolved in anhydrous acetone, then imidazole was added and stirred to dissolve. The mixture was then refluxed in an oil bath at 60-70°C for 12-15 hours. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed by vacuum distillation, and the product was washed and dried to obtain intermediate A. S2: Dissolve intermediate A in acetonitrile, add 1,3-propanesulfonic acid lactone, stir to dissolve, reflux at 80°C for 24 h under a protective atmosphere. After the reaction is complete, cool to room temperature, remove the solvent by vacuum distillation, wash three times with cold diethyl ether, and dry under vacuum to obtain the amphoteric monomer.

[0012] In this process, 4-vinylbenzyl chloride reacts with imidazole in anhydrous acetone via a nucleophilic substitution reaction. The nitrogen atom of the imidazole attacks the methylene carbon of the benzyl chloride, replacing the chlorine atom to generate intermediate A. Subsequently, intermediate A undergoes a quaternization reaction with 1,3-propanesulfonate lactone in acetonitrile. The nitrogen atom on the imidazole ring nucleophilically attacks the propyl terminal carbon atom of the propanesulfonate lactone, opening the ring to form a zwitterionic structure, ultimately yielding an imidazole-type amphoteric monomer containing vinyl groups, which simultaneously carry a positively charged imidazole onium group and a negatively charged sulfonate group. Its structure is shown below: In a more optimized manner, the raw materials for preparing intermediate A include the following components: by weight, 10-15 parts of 4-vinylbenzyl chloride, 80-100 parts of anhydrous acetone, and 10-15 parts of imidazole.

[0013] In a more optimized manner, the raw materials for preparing the amphoteric monomer include the following components: by weight, 8-10 parts of intermediate A, 80-100 parts of acetonitrile, and 5-8 parts of 1,3-propanesulfonic acid lactone.

[0014] More preferably, the conductive additive includes one or more of indium tin oxide with a particle size of 30-100 nm, zinc oxide with a particle size of 20-80 nm, and titanium dioxide with a particle size of 10-60 nm.

[0015] The beneficial effects of this invention are: Firstly, the modified filler uses vinyl-functionalized nano-silica as its core. Its surface undergoes free radical polymerization with vinyl groups, glycidyl methacrylate, maleic anhydride, and amphoteric monomers to form a grafted polymer layer. This polymer chain segment can generate stronger interfacial interactions with the polyester matrix molecular chains, effectively improving the compatibility between the inorganic filler and the organic polyester matrix, reducing filler agglomeration, ensuring the uniformity of the fiber structure, and providing a foundation for the stability of the material's mechanical properties.

[0016] Secondly, the amphoteric monomers introduced into the modified filler, containing positively charged imidazolium groups and negatively charged sulfonate groups, form an amphoteric structure. These polar groups can interact more strongly with disperse dye molecules (which usually contain polar groups) through electrostatic attraction, hydrogen bonding, and other mechanisms, increasing the adsorption sites and binding force of the dye in the fiber. At the same time, the epoxy groups of glycidyl methacrylate and the anhydride groups of maleic anhydride further enhance the polarity of the filler surface, promoting the penetration and fixation of dye molecules, thereby helping the fiber achieve a deep dyeing effect.

[0017] Thirdly, vinyl-functionalized nano-silica, as a rigid inorganic core, after polymer grafting modification, can be uniformly dispersed in the fiber matrix through nanoscale effects, and can also be tightly bound to the matrix through grafted segments, avoiding local performance fluctuations caused by uneven filler dispersion. This structure not only provides support for the uniform distribution of conductive additives (such as indium tin oxide and zinc oxide), ensuring the stability of conductivity, but also reduces structural defects in the fiber during processing or use through the synergistic effect of the filler and the matrix, indirectly improving the overall performance of the material. Detailed Implementation

[0018] 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.

[0019] Example 1: A method for preparing a deep-dyeable conductive fiber material, comprising the following steps: mixing dried polyester chips with modified filler and conductive additive (zinc oxide), producing masterbatch by twin-screw melt extrusion, followed by high-temperature spinning melt extrusion, cooling and solidification by ring blowing, performing three-step hot drawing, and finally oiling, web treatment, and winding into a yarn cake to obtain the deep-dyeable conductive fiber material; the mass ratio of polyester chips, modified filler and conductive additive is 85:5:2; The preparation process of the modified filler is as follows: Step 1: Mix 10 parts tetraethoxysilane, 80 parts anhydrous ethanol, 10 parts deionized water and 2 parts ammonia water, and stir magnetically for 3 hours at a constant temperature of 30°C. Then add 5 parts vinyltrimethoxysilane ethanol solution (20wt%) dropwise, and continue the reaction at the same temperature for 24 hours. After the reaction is completed, separate the product by centrifugation, wash and dry to obtain vinyl-functionalized nano silica. Step 2: Add 20 parts glycidyl methacrylate, 5 parts maleic anhydride and 5 parts amphoteric monomer to 100 parts N,N-dimethylformamide, adjust the pH to 5, add 10 parts vinyl-functionalized nano silica, stir evenly, add 1 part ammonium persulfate solution (5wt%) dropwise under a protective atmosphere, raise the temperature to 85℃, react for 3 hours, after the reaction is completed, perform post-treatment to obtain the modified filler; The preparation process of the amphoteric monomer is as follows: S1: Under a protective atmosphere, 10 parts of 4-vinylbenzyl chloride were dissolved in 80 parts of anhydrous acetone, and then 10 parts of imidazole were added. The mixture was stirred and dissolved, and then refluxed in an oil bath at 60°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed by vacuum distillation, and the mixture was washed and dried to obtain intermediate A. S2: Dissolve 8 parts of intermediate A in 80 parts of acetonitrile, add 5 parts of 1,3-propanesulfonic acid lactone, stir to dissolve, and reflux at 80°C for 24 h under a protective atmosphere. After the reaction is complete, cool to room temperature, remove the solvent by vacuum distillation, wash 3 times with cold diethyl ether, and dry under vacuum to obtain the amphoteric monomer.

[0020] Example 2: A method for preparing a deep-dyeable conductive fiber material, comprising the following steps: mixing dried polyester chips with modified filler and conductive additive (zinc oxide), producing masterbatch by twin-screw melt extrusion, followed by high-temperature spinning melt extrusion, cooling and solidification by ring blowing, performing three-step hot drawing, and finally oiling, web treatment, and winding into a yarn cake to obtain the deep-dyeable conductive fiber material; the mass ratio of polyester chips, modified filler and conductive additive is 95:6:3; The preparation process of the modified filler is as follows: Step 1: Mix 12 parts tetraethoxysilane, 100 parts anhydrous ethanol, 15 parts deionized water and 5 parts ammonia water, and stir magnetically for 4 hours at a constant temperature of 30°C. Then add 10 parts vinyltrimethoxysilane ethanol solution (20wt%) dropwise, and continue the reaction at the same temperature for 24 hours. After the reaction is completed, separate the product by centrifugation, wash and dry to obtain vinyl-functionalized nano silica. Step 2: Add 30 parts glycidyl methacrylate, 10 parts maleic anhydride and 15 parts amphoteric monomer to 150 parts N,N-dimethylformamide, adjust the pH to 5, add 20 parts vinyl-functionalized nano silica, stir evenly, add 3 parts ammonium persulfate solution (5wt%) dropwise under a protective atmosphere, raise the temperature to 90℃, react for 4 hours, after the reaction is completed, perform post-treatment to obtain the modified filler; The preparation process of the amphoteric monomer is as follows: S1: Under a protective atmosphere, 15 parts of 4-vinylbenzyl chloride were dissolved in 100 parts of anhydrous acetone, and then 15 parts of imidazole were added. The mixture was stirred and dissolved, and then refluxed in an oil bath at 70°C for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed by vacuum distillation, and the mixture was washed and dried to obtain intermediate A. S2: Dissolve 10 parts of intermediate A in 100 parts of acetonitrile, add 8 parts of 1,3-propanesulfonic acid lactone, stir to dissolve, and reflux at 80°C for 24 h under a protective atmosphere. After the reaction is complete, cool to room temperature, remove the solvent by vacuum distillation, wash 3 times with cold diethyl ether, and dry under vacuum to obtain the amphoteric monomer.

[0021] Example 3: A method for preparing a deep-dyeable conductive fiber material, comprising the following steps: mixing dried polyester chips with modified filler and conductive additive (zinc oxide), producing masterbatch by twin-screw melt extrusion, followed by high-temperature spinning melt extrusion, cooling and solidification by ring blowing, performing three-step hot drawing, and finally oiling, web treatment, and winding into a yarn cake to obtain the deep-dyeable conductive fiber material; the mass ratio of polyester chips, modified filler and conductive additive is 90:5.5:2.5; The preparation process of the modified filler is as follows: Step 1: Mix 11 parts tetraethoxysilane, 90 parts anhydrous ethanol, 12.5 parts deionized water and 3.5 parts ammonia water, and stir magnetically at a constant temperature of 30℃ for 3.5 h. Then add 7.5 parts vinyltrimethoxysilane ethanol solution (20 wt%) dropwise, and continue the reaction at the same temperature for 24 h. After the reaction is completed, separate the product by centrifugation, wash and dry to obtain vinyl-functionalized nano silica. Step 2: Add 25 parts glycidyl methacrylate, 7.5 parts maleic anhydride and 10 parts amphoteric monomer to 125 parts N,N-dimethylformamide, adjust the pH to 5, add 15 parts vinyl-functionalized nano silica, stir evenly, add 2 parts ammonium persulfate solution (5wt%) dropwise under a protective atmosphere, raise the temperature to 87.5℃, react for 3.5h, after the reaction is completed, post-process to obtain the modified filler; The preparation process of the amphoteric monomer is as follows: S1: Under a protective atmosphere, 12.5 parts of 4-vinylbenzyl chloride were dissolved in 90 parts of anhydrous acetone, and then 12.5 parts of imidazole were added. The mixture was stirred and dissolved, and then refluxed in an oil bath at 65°C for 13.5 h. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed by vacuum distillation, and the product was washed and dried to obtain intermediate A. S2: Dissolve 9 parts of intermediate A in 90 parts of acetonitrile, add 6.5 parts of 1,3-propanesulfonic acid lactone, stir to dissolve, and reflux at 80°C for 24 h under a protective atmosphere. After the reaction is complete, cool to room temperature, remove the solvent by vacuum distillation, wash 3 times with cold diethyl ether, and dry under vacuum to obtain the amphoteric monomer.

[0022] Comparative Example 1: Without introducing amphoteric monomers, as follows: A method for preparing a deep-dyeable conductive fiber material includes the following steps: mixing dried polyester chips with modified fillers and conductive additives (zinc oxide), producing masterbatch through twin-screw melt extrusion, followed by high-temperature spinning melt extrusion, cooling and solidification by ring blowing, performing three-step hot drawing, and finally oiling, web treatment, and winding into a yarn cake to obtain the deep-dyeable conductive fiber material; the mass ratio of polyester chips, modified fillers, and conductive additives is 90:5.5:2.5; The preparation process of the modified filler is as follows: Step 1: Mix 11 parts tetraethoxysilane, 90 parts anhydrous ethanol, 12.5 parts deionized water and 3.5 parts ammonia water, and stir magnetically at a constant temperature of 30℃ for 3.5 h. Then add 7.5 parts vinyltrimethoxysilane ethanol solution (20 wt%) dropwise, and continue the reaction at the same temperature for 24 h. After the reaction is completed, separate the product by centrifugation, wash and dry to obtain vinyl-functionalized nano silica. Step 2: Add 25 parts glycidyl methacrylate and 7.5 parts maleic anhydride to 125 parts N,N-dimethylformamide, adjust the pH to 5, add 15 parts vinyl-functionalized nano silica, stir evenly, add 2 parts ammonium persulfate solution (5wt%) dropwise under a protective atmosphere, raise the temperature to 87.5℃, and react for 3.5 h. After the reaction is completed, perform post-treatment to obtain the modified filler.

[0023] Comparative Example 2: No modified filler was introduced, as follows: A method for preparing a deep-dyeable conductive fiber material includes the following steps: mixing dried polyester chips with conductive additives, producing masterbatch by twin-screw melt extrusion, followed by high-temperature spinning melt extrusion, cooling and solidification by ring blowing, performing three-step hot stretching, and finally oiling, web treatment, and winding into a yarn cake to obtain the deep-dyeable conductive fiber material; the mass ratio of polyester chips to conductive additives is 90:2.5.

[0024] Testing experiment: (1) Tensile tests were performed on the finished products obtained in the examples and comparative examples in accordance with standard GB / T3923.1-2013; (2) Using conventional disperse dyes, dyeing was carried out under the conditions of a liquor ratio of 1:100, a dyeing temperature of 95°C, a dye concentration of 2% owf, a dyeing time of 50 min, and a pH value controlled at 4.5. The dyeing rate was measured. The obtained data is shown in the table below: Fracture strength (cN / dtex) 4.8 4.9 5.2 4.4 3.6 Dyeing rate (%) 92 91 95 81 73 Conclusion: This invention produces a deep-dyeing conductive fiber material by mixing polyester chips with modified fillers and conductive additives in a specific ratio, followed by twin-screw melt extrusion, high-temperature spinning, and three-step hot drawing processes. This material exhibits excellent mechanical and dyeing properties. The breaking strengths of Examples 1 to 3 were 4.8 cN / dtex, 4.9 cN / dtex, and 5.2 cN / dtex, respectively, with dye uptake rates of 92%, 91%, and 95%, significantly higher than Comparative Example 1 (breaking strength 4.4 cN / dtex, dye uptake 81%) and Comparative Example 2 (breaking strength 3.6 cN / dtex, dye uptake 73%). This indicates that the introduction of modified fillers significantly improves the mechanical and dyeing properties of the fiber. In particular, the addition of amphoteric monomers further optimizes the deep-dyeing effect by enhancing dye adsorption sites and interfacial interactions. Furthermore, the synergistic effect of vinyl-functionalized nano-silica and the grafted polymer layer ensures the uniform dispersion of the conductive additives and the stability of the fiber structure.

[0025] Therefore, the preparation method provided by this invention not only achieves high performance of conductive fiber materials, but also provides reliable technical support for their application in the field of functional textiles.

[0026] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0027] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A method for preparing a deep-dyeable conductive fiber material, characterized in that, Includes the following steps: The dried polyester chips are mixed with modified fillers and conductive additives, and then melt-extruded by a twin-screw extruder to produce a masterbatch. Subsequently, the masterbatch is melt-extruded by high-temperature spinning, cooled and solidified by a ring blower, and then subjected to three-step hot stretching. Finally, the masterbatch is oiled, networked, and wound into a yarn cake to obtain a deep-dyeable conductive fiber material. The conductive additives include one or more of indium tin oxide with a particle size of 30-100 nm and zinc oxide with a particle size of 20-80 nm. The preparation process of the modified filler is as follows: Step 1: Mix tetraethoxysilane, anhydrous ethanol, deionized water and ammonia, and stir magnetically at 30°C for 3-4 hours. Then add an ethanol solution of vinyltrimethoxysilane dropwise and continue the reaction at the same temperature for 24 hours. After the reaction is complete, separate the product by centrifugation, wash and dry to obtain vinyl-functionalized nano silica. Step 2: Add glycidyl methacrylate, maleic anhydride and amphoteric monomer to N,N-dimethylformamide, adjust the pH to 5, add vinyl-functionalized nano-silica, stir evenly, add ammonium persulfate solution dropwise under a protective atmosphere, raise the temperature to 85-90℃, react for 3-4 hours, after the reaction is completed, perform post-treatment to obtain the modified filler; The preparation process of the amphoteric monomer is as follows: S1: Under a protective atmosphere, 4-vinylbenzyl chloride was dissolved in anhydrous acetone, then imidazole was added and stirred to dissolve. The mixture was then refluxed in an oil bath at 60-70°C for 12-15 hours. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed by vacuum distillation, and the product was washed and dried to obtain intermediate A. S2: Dissolve intermediate A in acetonitrile, add 1,3-propanesulfonic acid lactone, stir to dissolve, reflux at 80°C for 24 h under a protective atmosphere. After the reaction is complete, cool to room temperature, remove the solvent by vacuum distillation, wash three times with cold diethyl ether, and dry under vacuum to obtain the amphoteric monomer.

2. The method for preparing a deep-dyeable conductive fiber material according to claim 1, characterized in that, The mass ratio of the polyester chips, modified fillers, and conductive additives is 85-95:5-6:2-3.

3. The method for preparing a deep-dyeable conductive fiber material according to claim 1, characterized in that, The raw materials for preparing the vinyl-functionalized nano silica include the following components: by weight, 10-12 parts of tetraethoxysilane, 80-100 parts of anhydrous ethanol, 10-15 parts of deionized water, 2-5 parts of ammonia, and 5-10 parts of an ethanol solution of vinyltrimethoxysilane; wherein the concentration of the ethanol solution of vinyltrimethoxysilane is 20 wt%.

4. The method for preparing a deep-dyeable conductive fiber material according to claim 1, characterized in that, The raw materials for preparing the modified filler include the following components: by weight, 20-30 parts glycidyl methacrylate, 5-10 parts maleic anhydride, 5-15 parts amphoteric monomer, 100-150 parts N,N-dimethylformamide, 10-20 parts vinyl-functionalized nano-silica, and 1-3 parts ammonium persulfate solution; wherein the concentration of the ammonium persulfate solution is 5 wt%.

5. The method for preparing a deep-dyeable conductive fiber material according to claim 1, characterized in that, The raw materials for preparing intermediate A include the following components: by weight, 10-15 parts of 4-vinylbenzyl chloride, 80-100 parts of anhydrous acetone, and 10-15 parts of imidazole.

6. The method for preparing a deep-dyeable conductive fiber material according to claim 1, characterized in that, The raw materials for preparing the amphoteric monomer include the following components: by weight, 8-10 parts intermediate A, 80-100 parts acetonitrile, and 5-8 parts 1,3-propanesulfonic acid lactone.

7. The deep-dyeable conductive fiber material obtained by the preparation method of a deep-dyeable conductive fiber material according to any one of claims 1-6.

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