CN112900079A - High-conductivity and environment-friendly aramid fiber and preparation method thereof - Google Patents
High-conductivity and environment-friendly aramid fiber and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
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- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to the technical field of conductive polymer composite materials, in particular to a high-conductivity and environment-friendly aramid fiber and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of conductive polymer composite materials, in particular to high-conductivity and environment-friendly aramid fiber and a preparation method thereof.
Background
Conductive materials are widely used for electrostatic protection and electromagnetic shielding. The traditional metal material can not meet the requirements of flexibility and strength at the same time, and the conductive polymer composite material can meet the requirements, so that the conductive polymer composite material has attracted much attention in recent years.
Aramid fiber is a high-performance polymer synthetic material, and has excellent performances of high strength, high modulus, high temperature resistance, flame retardance, chemical stability and the like. Can be used as an excellent base material. Therefore, the coating is widely applied to the fields of military industry, protection, industry and the like. The macromolecular structure of poly-p-phenylene terephthamide fiber (para-aramid fiber for short) is a high polymer which is similar to a rigid straight chain and formed by connecting amido bonds with para positions of benzene rings.
The aramid fiber has the advantages of being light and soft compared with a metal wire, and can be used for fiber blended products. However, due to the characteristics of smooth fiber surface, lack of active groups, low reactivity and the like, chemical plating metal is difficult to directly deposit on the fiber surface, the bonding force between the fiber and the metal plating layer is poor, and the metal plating layer is easy to fall off, so that the conductivity and the durability of the fiber are influenced. In the research on the preparation and performance of silver-plated conductive aramid fibers by Liang Jing et al, a metallization reagent (NaH-DMSO) is used in the silver plating process, and the reagent is flammable and explosive and cannot meet the requirement of large-scale industrial production. The invention patent 201310685423.7 entitled aramid silvering conductive fiber and preparation method thereof by flame et al uses traditional coarsening, sensitizing, activating and chemical silvering method, using 10-30g stannous chloride and 0.1-1g palladium chloride, but the operation process of the process is complicated, stannous chloride has certain harm to the environment, palladium belongs to noble metal and is expensive. CN103668944A discloses a preparation method of conductive aramid fiber, which comprises the following steps: the method comprises the steps of aramid fiber coarsening, aramid fiber hydrolysis, palladium salt activation, reduction, chemical silver plating, cleaning, drying and aramid silver plating fiber product. The method has the advantages that aramid fibers are easily damaged in the roughening process of the aramid fibers, and the fiber strength is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the highly conductive and environment-friendly aramid fiber and the preparation method thereof are provided, the aramid fiber is not damaged, the environment is not harmed, the conductivity is strong, and the silver layer has higher firmness.
In order to solve the technical problems, the invention adopts the technical scheme that the high-conductivity and environment-friendly aramid fiber comprises an aramid fiber body, an adhesion layer, an adsorption layer and a silver plating layer, wherein the adhesion layer is arranged on the surface of the aramid fiber body and used for enhancing the stability of the conductive aramid fiber in a water environment, the adsorption layer is used for being matched with the adhesion layer to adsorb silver ions, and the silver plating layer is arranged on the surface of the aramid fiber body.
According to the highly-conductive and environment-friendly aramid fiber, the aramid fiber body is meta-aramid fiber or para-aramid fiber.
The preparation method of the high-conductivity and environment-friendly aramid fiber comprises the following steps:
(1) cleaning the aramid fiber body, removing surface impurities and drying;
(2) modifying an aramid fiber body for 4-48 hours at a reaction temperature of 15-35 ℃ by using 1-8g/L of dopamine aqueous solution to obtain poly-dopamine modified aramid fibers;
(3) modifying the aramid fiber modified by the polydopamine for 2-10 hours at a reaction temperature of 20-80 ℃ by using a silane coupling agent aqueous solution to obtain the polydopamine/silane coupling agent modified aramid fiber;
(4) and (3) placing the modified aramid fiber into a prepared silver-ammonia solution, activating for 10-60 minutes, dropwise adding a reducing solution prepared in advance, reacting for 4-24 hours, washing with deionized water, and drying to obtain the aramid fiber with the silver layer coated on the surface.
According to the preparation method of the high-conductivity and environment-friendly aramid fiber, the cleaning condition in the step (1) is ultrasonic cleaning.
According to the preparation method of the high-conductivity and environment-friendly aramid fiber, the pH value of the dopamine hydrochloride solution in the step (2) is 8-9.
In the preparation method of the highly conductive and environment-friendly aramid fiber, the coupling agent in the step (3) is gamma-mercaptopropyltriethoxysilane or gamma-mercaptopropyltriethoxysilane.
In the preparation method of the high-conductivity and environment-friendly aramid fiber, the concentration of the coupling agent aqueous solution in the step (3) is 1-4% (mass fraction).
In the preparation method of the highly conductive and environment-friendly aramid fiber, the silver-ammonia solution in the step (3) is composed of ammonia water, a sodium hydroxide solution and a silver nitrate solution.
According to the preparation method of the high-conductivity and environment-friendly aramid fiber, the concentration of the silver nitrate solution in the step (4) is 5-30 g/L.
According to the preparation method of the high-conductivity and environment-friendly aramid fiber, the reducing solution in the step (4) is a glucose solution, and the concentration of the glucose solution is 10-40 g/L.
The highly conductive and environment-friendly aramid fiber and the preparation method thereof have the advantages that the aramid fiber is not damaged, the aramid fiber is harmless to the environment, the conductivity is strong, the surface resistance is 0.26 omega/cm, the silver layer has high firmness, and the aramid fiber still has good conductivity after being ultrasonically cleaned for 10 minutes.
Silane coupling agents are very effective for interface modification between inorganic-organic materials, but in the presence of water, the stability of the product is susceptible to hydrolysis of the metal-O-Si-C bond. The polydopamine contains a catechol structure, has strong adhesion capability in a water environment, and can overcome the problems existing when the coupling agent is used alone when being used together with the coupling agent. Therefore, according to the method for secondary functionalization by combining dopamine modification with a sulfhydryl coupling agent, firstly, a polydopamine modification layer with strong adhesion capacity is introduced to the surface of aramid fiber, then, modification is further performed through the sulfhydryl coupling agent on the basis, a sulfhydryl functional group is introduced to the surface of the aramid fiber, and the adsorption rate of silver ions on the surface of the aramid fiber in the chemical silver plating process is improved by utilizing the adsorption effect of sulfydryl on metal ions, so that the silver content is further improved. In addition, the formed sulfydryl-silver bond can enhance the combination effect between the aramid fiber and the silver nanoparticles, thereby improving the fastness of the silver coating.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
The utility model provides a high electrically conductive, aramid fiber of environmental protection, includes the aramid fiber body, locates being used for on aramid fiber body surface in the water environment, the adhesion layer of reinforcing electrically conductive aramid fiber stability for carry out absorbent adsorption layer to silver ion with the adhesion layer cooperation, and silvering layer. The adhesion layer is a polydopamine modification layer, and the adsorption layer is a silane coupling agent modification layer.
The aramid fiber body is meta-aramid fiber or para-aramid fiber.
The preparation method of the high-conductivity and environment-friendly aramid fiber comprises the following steps:
(1) cleaning the aramid fiber body, removing surface impurities and drying;
(2) modifying an aramid fiber body for 4 hours at a reaction temperature of 15 ℃ by using a 1g/L dopamine aqueous solution, washing for 3 times by using deionized water, and drying to obtain poly-dopamine modified aramid fibers;
(3) modifying the aramid fiber modified by the polydopamine at a reaction temperature of 20 ℃ for 2 hours by using a silane coupling agent aqueous solution, washing the aramid fiber by using deionized water for 3 times, and drying to obtain the polydopamine/silane coupling agent modified aramid fiber;
(4) and (2) placing the modified aramid fiber into a prepared silver-ammonia solution, activating for 10 minutes, dropwise adding a reducing solution prepared in advance, reacting for 4 hours, washing for 3 times by using deionized water, and then drying in vacuum at 60 ℃ for 24 hours to obtain the aramid fiber with the surface coated with the silver layer.
The cleaning condition in the step (1) is ultrasonic cleaning.
The pH value of the dopamine hydrochloride solution in the step (2) is 8-9.
The coupling agent in the step (3) is gamma-mercaptopropyl-trimethoxysilane.
The concentration of the coupling agent aqueous solution in the step (3) is 1% (mass fraction).
The silver-ammonia solution in the step (3) consists of ammonia water, a sodium hydroxide solution and a silver nitrate solution. The preparation method comprises the steps of dropwise adding ammonia water into a silver nitrate solution until the solution is clear, adjusting the pH value to 11-12 by using a sodium hydroxide solution, and continuously dropwise adding ammonia water until the solution is clear.
The concentration of the silver nitrate solution in the step (4) is 5 g/L.
The reducing solution in the step (4) is glucose solution, and the concentration of the reducing solution is 10 g/L. Heating to boil for 10 min, and naturally cooling to room temperature.
Example 2
The same parts of this embodiment as those of embodiment 1 are not described again, but the differences are as follows: the preparation method of the high-conductivity and environment-friendly aramid fiber comprises the following steps:
(1) cleaning the aramid fiber body, removing surface impurities and drying;
(2) modifying an aramid fiber body for 20 hours at a reaction temperature of 20 ℃ by using a 5g/L dopamine aqueous solution to obtain poly-dopamine modified aramid fibers;
(3) modifying the aramid fiber modified by the polydopamine at a reaction temperature of 50 ℃ for 8 hours by using a silane coupling agent aqueous solution, washing the aramid fiber by using deionized water for 3 times, and drying to obtain the polydopamine/silane coupling agent modified aramid fiber;
(4) and (2) placing the modified aramid fiber into a prepared silver-ammonia solution, activating for 50 minutes, dropwise adding a reducing solution prepared in advance, reacting for 10 hours, washing for 3 times by using deionized water, and then drying in vacuum at 60 ℃ for 24 hours to obtain the aramid fiber with the surface coated with the silver layer.
The coupling agent in the step (3) is gamma-mercaptopropyltriethoxysilane.
The concentration of the coupling agent aqueous solution in the step (3) is 2.5% (mass fraction).
The concentration of the silver nitrate solution in the step (4) is 10 g/L.
The reducing solution in the step (4) is glucose solution, and the concentration of the reducing solution is 20 g/L.
Example 3
The same parts of this embodiment as those of embodiment 2 are not described again, but the differences are as follows: the preparation method of the high-conductivity and environment-friendly aramid fiber comprises the following steps:
(1) cleaning the aramid fiber body, removing surface impurities and drying;
(2) modifying an aramid fiber body for 48 hours at the reaction temperature of 35 ℃ by using 8g/L of dopamine aqueous solution to obtain poly-dopamine modified aramid fibers;
(3) modifying the aramid fiber modified by the polydopamine for 10 hours at a reaction temperature of 80 ℃ by using a silane coupling agent aqueous solution, washing for 3 times by using deionized water, and drying to obtain the polydopamine/silane coupling agent modified aramid fiber;
(4) and (2) placing the modified aramid fiber into a prepared silver-ammonia solution, activating for 60 minutes, dropwise adding a reducing solution prepared in advance, reacting for 24 hours, washing for 3 times by using deionized water, and then drying in vacuum at 60 ℃ for 24 hours to obtain the aramid fiber with the surface coated with the silver layer.
The concentration of the coupling agent aqueous solution in the step (3) is 4% (mass fraction).
The concentration of the silver nitrate solution in the step (4) is 30 g/L.
The reducing solution in the step (4) is glucose solution, and the concentration of the reducing solution is 40 g/L.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and that various changes, modifications, additions and substitutions which are within the spirit and scope of the present invention and which can be made by those skilled in the art are also within the scope of the present invention.
Claims (10)
1. The highly conductive and environment-friendly aramid fiber is characterized in that: the silver ion adsorption device comprises an aramid fiber body, an adhesion layer, an adsorption layer and a silver coating, wherein the adhesion layer is arranged on the surface of the aramid fiber body and used for enhancing the stability of the conductive aramid fiber in a water environment, and the adsorption layer is used for being matched with the adhesion layer to adsorb silver ions.
2. The highly conductive and environment-friendly aramid fiber as claimed in claim 1, wherein the aramid fiber body is a meta-aramid fiber or a para-aramid fiber.
3. A method for preparing the highly conductive, environmentally friendly aramid fiber as claimed in claim 1 or 2, characterized in that: the method comprises the following steps:
(1) cleaning the aramid fiber body, removing surface impurities and drying;
(2) modifying an aramid fiber body for 4-48 hours at a reaction temperature of 15-35 ℃ by using 1-8g/L of dopamine aqueous solution to obtain poly-dopamine modified aramid fibers;
(3) modifying the aramid fiber modified by the polydopamine for 2-10 hours at a reaction temperature of 20-80 ℃ by using a silane coupling agent aqueous solution to obtain the polydopamine/silane coupling agent modified aramid fiber;
(4) and (3) placing the modified aramid fiber into a prepared silver-ammonia solution, activating for 10-60 minutes, dropwise adding a reducing solution prepared in advance, reacting for 4-24 hours, washing with deionized water, and drying to obtain the aramid fiber with the silver layer coated on the surface.
4. The preparation method of the highly conductive and environment-friendly aramid fiber as claimed in claim 3, wherein the cleaning condition in the step (1) is ultrasonic cleaning.
5. The preparation method of the highly conductive and environment-friendly aramid fiber as claimed in claim 4, wherein the pH value of the dopamine hydrochloride solution in the step (2) is 8-9.
6. The preparation method of the highly conductive and environment-friendly aramid fiber according to claim 5, wherein the coupling agent in the step (3) is gamma-mercaptopropyltriethoxysilane or gamma-mercaptopropyltriethoxysilane.
7. The preparation method of the highly conductive and environment-friendly aramid fiber as claimed in claim 6, wherein the concentration of the aqueous solution of the coupling agent in the step (3) is 1-4% (mass fraction).
8. The preparation method of the highly conductive and environment-friendly aramid fiber as claimed in claim 7, wherein the silver-ammonia solution in the step (3) is composed of ammonia water, a sodium hydroxide solution and a silver nitrate solution.
9. The preparation method of the highly conductive and environment-friendly aramid fiber as claimed in claim 8, wherein the concentration of the silver nitrate solution in the step (4) is 5-30 g/L.
10. The preparation method of the highly conductive and environment-friendly aramid fiber as claimed in claim 9, wherein the reducing solution in the step (4) is a glucose solution with a concentration of 10-40 g/L.
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Cited By (2)
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| WO2023082090A1 (en) * | 2021-11-10 | 2023-05-19 | 青岛科技大学 | Dendritic silver-plated aramid electrically conductive filler and preparation method therefor and application thereof, and polymer/dendritic silver-plated aramid composite material |
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Application publication date: 20210604 |