CN110184809B - Thermal shock resistant conductive polyimide fiber and preparation method thereof - Google Patents

Thermal shock resistant conductive polyimide fiber and preparation method thereof Download PDF

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CN110184809B
CN110184809B CN201910516451.3A CN201910516451A CN110184809B CN 110184809 B CN110184809 B CN 110184809B CN 201910516451 A CN201910516451 A CN 201910516451A CN 110184809 B CN110184809 B CN 110184809B
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polyimide fiber
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杜志军
邱雪鹏
董志鑫
代学民
矫龙
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Changchun Institute of Applied Chemistry of CAS
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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
    • D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic System
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    • 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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    • 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
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
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    • 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

Abstract

The invention provides a thermal shock resistant conductive polyimide fiber and a preparation method thereof, the fiber comprises a modified polyimide fiber, a metal transition layer and a metal coating which are sequentially compounded on the surface of the modified polyimide fiber, the surface of the modified polyimide fiber is modified by a pyridine derivative or a quinoline derivative, the metal in the metal transition layer is selected from copper, nickel or silver, the metal in the metal coating is selected from copper, nickel or silver, the polyimide fiber is used as a base fiber, the surface of the polyimide fiber is modified by the pyridine derivative or the quinoline derivative, the transition layer containing the pyridine derivative or the quinoline derivative is introduced between the surface of the polyimide fiber and the coating through a covalent bond and a coordination bond to play a role of soft connection, the bonding performance of the fiber and the metal is improved by utilizing the strong forces of the pyridine, the amido bond and the metal, so that the thermal shock resistance of the fiber is improved, the electrical conductivity is higher, and the electrical conductivity of the fiber is 1.154～5.0×104S/cm; no metal falling off after 10 times of circulation at-180 to 200 ℃.

Description

Thermal shock resistant conductive polyimide fiber and preparation method thereof
Technical Field
The invention belongs to the technical field of polyimide fibers, and particularly relates to a thermal shock resistant conductive polyimide fiber and a preparation method thereof.
Background
Technological progress has led to the popularization of electronic products, and electromagnetic pollution is accompanied therewith. Electromagnetic radiation, noise pollution, water vapor pollution and air pollution are called as four public hazards of human beings, and threaten human survival. On one hand, the high-energy radiation is applied to a plurality of fields such as medicine, military, electron and the like; on the other hand, when applied to daily life of people as electronic equipment, electromagnetic radiation causes inevitable harm to human health. The metal plate, the metal mesh, the metal wire, the metalized fabric and the like have good conductive performance and magnetic conductivity, so that the metal plate, the metal mesh, the metal wire, the metalized fabric and the like have good electromagnetic shielding performance. The conductive fiber has flexibility, and also has the performances of electric conduction, static resistance, heat conduction and electromagnetic shielding, and is increasingly widely applied to national economy, such as conductive nets and working clothes in the electronic and electric power industry; electric heating clothes and electric heating bandages in the medical industry; electronic shielding cases in the aviation, aerospace and electronic industries, and the like. The conductive fiber can be used in the fields of antistatic textiles, electromagnetic radiation prevention textiles, intelligent textiles, military textiles and the like.
The conductive fiber is divided according to conductive components and the distribution state of the conductive components in the fiber, and mainly comprises the following components: metal fibers, carbon fibers, conductive polymer fibers, conductive component non-conductive polymer composite fibers, conductive component coated non-conductive polymer fibers, and the like. The metal fiber has good conductivity, heat resistance and chemical corrosion resistance, but for textiles, the metal fiber has small cohesive force, poor spinning performance and limited finished product color, is mainly used for carpets and working clothes fabrics, and is expensive when being made into high-fineness fibers; the carbon fiber has good conductivity, heat resistance and chemical resistance, but has high modulus, no toughness, no bending resistance, no heat shrinkage capability and limited application range; among the conductive polymer fibers, organic conductive fibers prepared by directly spinning polymer conductive materials such as polyacetylene, polyaniline, polypyrrole, polythiophene and the like are difficult to spin, have higher price and are difficult to widely use in textiles; the conductive component and the non-conductive polymer composite fiber have large conductive component addition amount and general electromagnetic shielding performance and are mainly used for static resistance; the conductive component coated non-conductive polymer type fiber has good conductive performance and shielding performance, but has the defect that the conductive layer is easy to fall off when the conductive component coated non-conductive polymer type fiber is used in a large temperature difference range, and particularly the metal coated non-conductive polymer type fiber has poor thermal shock resistance, which is mainly caused by large difference of thermal expansion coefficients. Even so, the metal-coated organic fiber is still a very important type of conductive fiber, which not only has good functions of electric conduction, heat conduction, reflection and electromagnetic wave absorption, but also has the characteristics of light weight, flexibility and air permeability. At present, the research and application of metal-coated organic fibers are mainly focused on traditional fibers, and as a high-performance fiber, the research on the surface metallization of a polyimide fiber is less.
The method for metalizing the surface of the organic fiber comprises vacuum evaporation, ion spraying, magnetron sputtering plating, electroplating and chemical plating. The vacuum evaporation has the advantages of convenient operation, high film forming speed, high efficiency and the like, but the initial energy of metal particles evaporated by the method is small, and the metal is deposited on the surface of the fiber in the form of atomic groups, so that the bonding strength of a coating and the fiber is poor, the coating has more vacuum and loose structure, and the method has high requirement on equipment and is difficult to control the deposition rate, so the method is generally only adopted when the fiber with special purposes is processed. Ion plating is to deposit evaporated metal atoms on the surface of fiber in ion form after electron impact ionization by using a certain plasma ionization technology under vacuum condition to form a film. The method combines the process advantages of high deposition rate of vacuum evaporation and good film bonding degree of a cathode sputtering technology, but the application of the ion spraying method to fibers and fabrics is less due to the structural instability of the fibers at high temperature and the dimensional instability of the fibers at high pressure. Magnetron sputtering is a high-speed low-temperature sputtering technology, and is characterized by high film forming rate, low substrate temperature, good film adhesion, capability of realizing large-area film coating, good process repeatability, convenience for automation and high processing cost. The electroplating method can generate a large amount of industrial wastewater and has great pollution. Electroless plating, also known as electroless plating or autocatalytic plating, is a plating method in which metal ions in a plating solution are reduced to metal by means of a suitable reducing agent and deposited onto the surface of a part in the absence of an applied current. Chemical plating is a novel surface treatment technology, and the technology is increasingly concerned by people with simple and convenient process, energy conservation and environmental protection. The method has the advantages of simple equipment, low energy consumption, no damage to the fibers, continuous treatment of the fibers and excellent electrical conductivity and thermal conductivity of the obtained fibers.
In patent CN101446037B, we disclose a method for preparing conductive polyimide fiber, which comprises coarsening with potassium permanganate and sodium hydroxide, sensitizing with stannous chloride, activating with silver ammonia solution, and performing conventional chemical plating to obtain copper-plated and nickel-plated fiber. The method has the advantages of high preparation reliability and controllable coating thickness, but the thermal shock resistance of the metal-plated fiber is poor, and the phenomenon of coating metal falling off is found to be serious after 4 times of cyclic experiments at room temperature to 200 ℃, as shown in figure 1. Patent CN101775670B discloses a method for preparing polyimide/silver composite conductive fiber by integrated molding. Firstly, preparing polyamic acid fiber by using polyamic acid solution, then carrying out ion exchange by using soluble silver salt solution to obtain polyamic acid silver compound, and obtaining silver-plated polyimide fiber by a thermal reduction method. The method has the advantages of integrated molding, simple process flow, few steps and low cost. However, since the catalytic degradation by the post-drawing and thermal reduction process cannot be performed, a conductive fiber having high strength cannot be obtained and the plating layer is thin. Patent CN107313249A discloses a polyimide/nickel composite conductive fiber and a preparation method thereof, which comprises treating polyimide fiber with strong alkali solution, performing ion exchange with soluble nickel or silver or palladium salt solution, then treating with a reducing agent to obtain polyimide fiber with the surface coated with an ultrathin metal particle layer, and finally obtaining nickel-plated polyimide fiber by a traditional chemical plating method. The method is not much different from the method disclosed in patent CN101446037B, both methods are activated after being treated by strong alkali, the method disclosed in patent CN101446037B is that stannous chloride serving as a reducing agent is adsorbed on the surface of a fiber at first, then the fiber with a silver ammonia solution or palladium chloride hydrochloric acid solution is treated to obtain a fiber with a silver or palladium metal particle layer coated on the surface, the method disclosed in patent CN107313249A is that nickel or silver or palladium ions are adsorbed on the surface of the fiber through ion exchange and then reduced by the reducing agent, and the final chemical plating methods are basically the same. Patent CN106702356A discloses a conductive polyimide fiber and its product and preparation method, which comprises subjecting the fiber to alkali treatment to obtain a fiber with carboxyl on the surface, then treating with cysteamine or cysteamine hydrochloride solution, then reducing divalent palladium ions with sulfydryl to obtain a fiber with metal palladium coated on the surface, and finally plating nickel, silver or copper by traditional chemical plating method. The method is basically the same as the method disclosed in patent CN101446037B, except that the reducing agent stannous chloride is replaced by cysteamine.
The above patents have a common disadvantage of poor thermal shock resistance when used over a wide temperature range, thereby limiting their use as high performance fibers.
Disclosure of Invention
In view of the above, the present invention aims to provide a thermal shock resistant conductive polyimide fiber and a preparation method thereof, wherein the fiber has high thermal shock resistance.
The invention provides a thermal shock resistant conductive polyimide fiber, which comprises a modified polyimide fiber;
and a metal transition layer and a metal coating layer which are sequentially compounded on the surface of the modified polyimide fiber;
the surface of the modified polyimide fiber is modified by a pyridine derivative or a quinoline derivative;
the metal in the metal transition layer is selected from copper, nickel or silver;
the metal in the metal plating layer is selected from copper, nickel or silver.
Preferably, the pyridine derivative is selected from formula 101, formula 102, formula 103, or formula 104; the quinoline derivative is selected from formula 105;
Figure BDA0002095200390000031
Figure BDA0002095200390000041
preferably, the metal in the metal transition layer and the metal plating layer is the same metal.
The invention provides a preparation method of a thermal shock resistant conductive polyimide fiber in the technical scheme, which comprises the following steps:
performing alkaline treatment on the polyimide fiber, and cleaning to obtain the polyimide fiber with the surface containing carboxylate;
putting the polyimide fiber with the carboxylate on the surface into a solution of a pyridine derivative or a quinoline derivative for reaction, and cleaning to obtain the polyimide fiber with the pyridine derivative or the quinoline derivative on the surface;
placing the polyimide fiber with the surface containing the pyridine derivative or the quinoline derivative in a soluble metal salt aqueous solution to complex metal ions to obtain the polyimide fiber with the surface containing the metal ions;
reducing and cleaning the polyimide fiber with the surface containing metal ions to obtain the polyimide fiber with the surface compounded with the metal transition layer;
and placing the polyimide fiber with the surface compounded with the metal transition layer into a plating solution for chemical plating to obtain the thermal shock resistant conductive polyimide fiber.
Preferably, the substance adopted by the alkaline treatment is potassium hydroxide solution; the temperature of the alkaline treatment is 20-60 ℃; the time of alkaline treatment is 10-30 min.
Preferably, the reaction temperature is 60-100 ℃; the reaction time is 5-30 min.
Preferably, the aqueous soluble metal salt solution is selected from one or more of copper sulfate, copper nitrate, silver nitrate, nickel nitrate and nickel sulfate;
the concentration of the soluble metal salt water solution is 0.1-0.6 mol/L;
the complexing temperature is 20-30 ℃; the complexing time is 5-30 min.
Preferably, the reducing agent used for the reduction is selected from any one or more of stannous chloride, dimethylamino borane, sodium hypophosphite, hydrazine hydrate, sodium ascorbate, formaldehyde and formic acid;
the reduction temperature is 10-50 ℃; the reduction time is 1-30 min.
The invention provides a thermal shock resistant conductive polyimide fiber, which comprises a modified polyimide fiber; and a metal transition layer and a metal coating layer which are sequentially compounded on the surface of the modified polyimide fiber; the surface of the modified polyimide fiber is modified by a pyridine derivative or a quinoline derivative; the metal in the metal transition layer is selected from copper, nickel or silver; the metal in the metal plating layer is selected from copper, nickel or silver. The fiber provided by the invention takes the polyimide fiber as the base fiber, the surface of the polyimide fiber is modified by pyridine derivatives or quinoline derivatives, and the polyimide fiber surface and the plating layer metal are introduced by covalent bonds and coordination bondsThe transition layer containing pyridine derivatives or quinoline derivatives plays a role of soft connection, and simultaneously the strong action of the pyridine derivatives, amido bonds and metals is utilized to improve the bonding performance of the fibers and the metals, so that the thermal shock resistance of the conductive fibers is improved4～5.0×104S/cm; no metal falling off after 10 times of circulation at minus 180 ℃ to 200 ℃.
Drawings
FIG. 1 shows the results of a thermal shock resistance test of a polyimide fiber according to a comparative example of the present invention;
FIG. 2 is a thermal shock resistance test chart of the copper-plated polyimide fiber prepared in example 1 of the present invention;
FIG. 3 is a thermal shock resistance test chart of the silver-plated polyimide fiber prepared in example 3 of the present invention;
FIG. 4 is a thermal shock resistance test chart of the nickel-plated polyimide fiber prepared in example 5 of the present invention.
Detailed Description
The invention provides a thermal shock resistant conductive polyimide fiber, which comprises a modified polyimide fiber;
and a metal transition layer and a metal coating layer which are sequentially compounded on the surface of the modified polyimide fiber;
the surface of the modified polyimide fiber is modified by a pyridine derivative or a quinoline derivative;
the metal in the metal transition layer is selected from copper, nickel or silver;
the metal in the metal plating layer is selected from copper, nickel or silver.
The fiber provided by the invention takes the polyimide fiber as a base fiber, the surface of the polyimide fiber is modified by the pyridine derivative or the quinoline derivative, a transition layer containing the pyridine derivative or the quinoline derivative is introduced between the surface of the polyimide fiber and a plating layer metal through a covalent bond and a coordination bond to play a role of soft connection, and the bonding performance of the fiber and the metal is improved by utilizing the strong action force of the pyridine, an amido bond and the metal, so that the thermal shock resistance of the conductive fiber is improved. The fibers also have high electrical conductivity.
The invention has wide application range, is suitable for polyimide fibers of various systems, is suitable for continuous production, not only effectively upgrades the use performance of the conductive polyimide fibers, but also provides guarantee for upgrading and upgrading of related products. The conductive polyimide fiber prepared by the invention has low loss rate of mechanical properties, good conductive performance and electromagnetic shielding performance, and can be applied to multiple fields of static prevention, shielding and the like.
The thermal shock resistant conductive polyimide fiber provided by the invention comprises a modified polyimide fiber, wherein the surface of the modified polyimide fiber is modified by a pyridine derivative or a quinoline derivative. In the present invention, the polyimide fiber has an average diameter of 18um and a linear density of 300D/0.1K.
In the present invention, the pyridine derivative is selected from formula 101, formula 102, formula 103, or formula 104; the quinoline derivative is selected from formula 105;
Figure BDA0002095200390000061
the thermal shock resistant conductive polyimide fiber provided by the invention comprises a metal transition layer and a metal coating which are sequentially compounded on the surface of the modified polyimide fiber. The metal in the metal transition layer is preferably selected from copper, nickel or silver; the metal plating layer is selected from copper, nickel or silver. The metal in the metal plating layer and the metal transition layer is preferably the same metal; the same metal is chosen to avoid additional thermal stress in the bimetallic layer due to differences in thermal expansion coefficients.
The invention provides a preparation method of a thermal shock resistant conductive polyimide fiber in the technical scheme, which comprises the following steps:
performing alkaline treatment on the polyimide fiber, and cleaning to obtain the polyimide fiber with the surface containing carboxylate;
putting the polyimide fiber with the carboxylate on the surface into a solution of a pyridine derivative or a quinoline derivative for reaction, and cleaning to obtain the polyimide fiber with the pyridine derivative or the quinoline derivative on the surface;
placing the polyimide fiber with the surface containing the pyridine derivative or the quinoline derivative in a soluble metal salt aqueous solution to complex metal ions to obtain the polyimide fiber with the surface containing the metal ions;
reducing and cleaning the polyimide fiber with the surface containing metal ions to obtain the polyimide fiber with the surface compounded with the metal transition layer;
and placing the polyimide fiber with the surface compounded with the metal transition layer into a plating solution for chemical plating to obtain the thermal shock resistant conductive polyimide fiber.
The invention carries out alkaline treatment on the polyimide fiber to obtain the polyimide fiber with the surface containing carboxylate. In the present invention, the substance used for the alkaline treatment is preferably potassium hydroxide solution; the concentration of the potassium hydroxide solution is 1-3 mol/L. The temperature of the alkaline treatment is preferably 20-60 ℃; the time of alkaline treatment is 10-30 min. The invention preferably employs deionized water for cleaning. The mass of the polyimide fiber and the volume ratio of substances adopted in the alkaline treatment are (200-300) mg: (40-50) mL.
After the polyimide fiber with the surface containing the carboxylate is obtained, the polyimide fiber with the surface containing the carboxylate is placed in a solution of a pyridine derivative or a quinoline derivative for reaction and is washed, and the polyimide fiber with the surface containing the pyridine derivative or the quinoline derivative is obtained. In the present invention, the solvent in the solution of the pyridine derivative or quinoline derivative is preferably selected from one or more of water, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. The concentration of the solution of the pyridine derivative or the quinoline derivative is preferably 0.5-2 mol/L. The reaction temperature is preferably 60-100 ℃, and the reaction time is preferably 5-30 min. After the reaction is finished, deionized water is preferably adopted for cleaning; and the cleaning is thorough.
The pyridine derivative is selected from formula 101, formula 102, formula 103 or formula 104; the quinoline derivative is selected from formula 105;
Figure BDA0002095200390000071
in the present invention, the pyridine derivative having the structure of formula 102 is preferably prepared according to the following steps:
mixing 2-aminopyridine, triethylamine and dichloromethane, and dropwise adding 2-chloroacetyl chloride for reaction to obtain the pyridine derivative with the structure of formula 102.
The pyridine derivative having the structure of formula 103 is preferably prepared according to the following steps:
mixing 3-aminopyridine, triethylamine and dichloromethane, and dropwise adding 2-chloroacetyl chloride for reaction to obtain the pyridine derivative with the structure of formula 103.
The pyridine derivative having the structure of formula 104 is preferably prepared according to the following steps:
mixing 4-aminopyridine, triethylamine and dichloromethane, and dropwise adding 2-chloroacetyl chloride for reaction to obtain the pyridine derivative with the structure of formula 104.
The quinoline derivative with the structure of formula 105 is preferably prepared according to the following steps:
mixing 8-aminoquinoline, triethylamine and dichloromethane, and dropwise adding 2-chloroacetyl chloride for reaction to obtain the quinoline derivative with the structure of formula 105.
After the polyimide fiber with the surface containing the pyridine derivative or the quinoline derivative is obtained, the polyimide fiber with the surface containing the pyridine derivative or the quinoline derivative is placed in a soluble metal salt aqueous solution to complex metal ions, and the polyimide fiber with the surface containing the metal ions is obtained. In the present invention, the aqueous soluble metal salt solution is selected from one or more of copper sulfate, copper nitrate, silver nitrate, nickel nitrate and nickel sulfate; the concentration of the soluble metal salt water solution is preferably 0.1-0.6 mol/L; the temperature of the complexation is preferably 20-30 ℃; the complexing time is preferably 5-30 min.
After complexing, deionized water is preferably adopted for cleaning, and cleaning is thorough.
After the polyimide fiber with the surface containing the metal ions is obtained, the polyimide fiber with the surface containing the metal ions is reduced and cleaned to obtain the polyimide fiber with the surface compounded with the metal transition layer. In the invention, the reducing agent used for the reduction is selected from any one or more of stannous chloride, dimethylamino borane, sodium hypophosphite, hydrazine hydrate, sodium ascorbate, formaldehyde and formic acid. The concentration of the reducing agent is preferably 0.01-2 mol/L; the reduction temperature is 10-50 ℃; the reduction time is 1-30 min. After reduction, the steel is preferably rinsed with deionized water. The metal transition layer is an ultrathin metal particle layer.
After the polyimide fiber with the surface compounded with the metal transition layer is obtained, the polyimide fiber with the surface compounded with the metal transition layer is placed in a plating solution for chemical plating to obtain the thermal shock resistant conductive polyimide fiber. The invention adopts the conventional chemical plating method to carry out chemical plating; the plating solution is a conventional electroless plating solution. The chemical plating temperature is 20-70 ℃. And preferably cleaning the polyimide fiber by using deionized water after chemical plating, and heating and air-drying the polyimide fiber to obtain the thermal shock resistant conductive polyimide fiber.
For further illustration of the present invention, the following examples are provided to describe a thermal shock resistant conductive polyimide fiber and its preparation method in detail, but they should not be construed as limiting the scope of the present invention.
Preparatory example 1
A pyridine derivative of the structure of formula 102: 2-aminopyridine (47.0g,0.5mol) and triethylamine (104.2mL,0.75mol) were dissolved in dichloromethane (300.0mL), 2-chloroacetyl chloride (62.1g,0.55mol) was added dropwise at 0 ℃ to 20 ℃ while controlling the reaction temperature, and then the reaction was carried out at room temperature for 3 hours. Water (100.0mL) was added and stirring was continued for 1h to separate the aqueous phase, the organic phase was washed with saturated aqueous sodium bicarbonate (100.0mL), the organic phase was dried over anhydrous sodium sulfate, the drying agent was filtered off, the dichloromethane was distilled off and dried under vacuum to give a reddish solid (76.8g, yield: 90%).1H NMR(400MHz,CDCl3):δ4.20(s,2H),7.10–7.09(m,1H),7.77–7.72(m,1H),8.20(d,1H,J＝4.4Hz),8.32–8.31(m,2H),8.93(s,1H)。
Preparatory example 2
A pyridine derivative of the structure of formula 103: 3-aminopyridine is used as a reaction raw material, the preparation process is the same as the formula 102, the product is white solid, and the yield is as follows: 80.2g, yield: 94 percent.1H NMR(400MHz,D2O):δ9.16(d,J＝3Hz,1H),8.42(d,1H,J＝6Hz),8.40(d,1H,J＝9Hz),7.90(dd,1H,J＝9Hz,6Hz),4.25(s,2H)。
Preparatory example 3
A pyridine derivative of the structure of formula 104: 4-aminopyridine (47.0g,0.5mol) and triethylamine (104.2mL,0.75mol) were dissolved in dichloromethane (300.0mL), 2-chloroacetyl chloride (62.1g,0.55mol) was added dropwise at 0 ℃ to 20 ℃ while controlling the reaction temperature, and after completion of the addition, the reaction was carried out at room temperature for 6 hours. Water (100.0mL) was added and stirring was continued for 1h to separate the aqueous phase, the organic phase was washed with saturated aqueous sodium bicarbonate (100.0mL), the organic phase was dried over anhydrous sodium sulfate, the drying agent was filtered off, the dichloromethane was evaporated and dried in vacuo to give a white solid (77.6g, yield: 91%).1H NMR(400MHz,CDCl3):δ4.20(s,2H),8.05(d,2H,J＝7.2),8.50(d,2H,J＝7.00),11.55(s,1H)。
Preparatory example 4
A pyridine derivative of the structure of formula 105: 8-aminoquinoline (72.1g,0.5mol) and triethylamine (104.2mL,0.75mol) were dissolved in dichloromethane (500.0mL), 2-chloroacetyl chloride (62.1g,0.55mol) was added dropwise at 0 ℃ to 20 ℃ while controlling the reaction temperature, and then the reaction was carried out at room temperature for 3 hours. Water (150.0mL) was added and stirring was continued for 1h to separate the aqueous phase, the organic phase was washed with saturated aqueous sodium bicarbonate (150.0mL), the organic phase was dried over anhydrous sodium sulfate, the drying agent was filtered off, after methylene chloride was evaporated, petroleum ether (200.0mL) was added, the mixture was stirred for 30min and filtered, and vacuum drying was carried out to give a reddish solid (107.0g, yield: 97%).1H NMR(400MHz,CDCl3):δ4.43–4.22(m,2H),7.50–7.40(m,1H),7.52(dd,J＝6.9,3.7Hz,2H),8.16(d,J＝8.3Hz,1H),8.80–8.69(m,1H),8.96–8.80(m,1H),9.97(s,1H)。
Comparative example
The invention relates to copper-plated polyimide fibers prepared according to the method disclosed in patent CN 101446037B.
The thermal shock resistance experiments of the copper-plated polyimide fiber prepared in the comparative example after circulating for 4 times from room temperature to 200 ℃ are compared, and the thermal shock resistance experiments are shown in fig. 1, wherein fig. 1 is a thermal shock resistance test result of the copper-plated polyimide fiber prepared in the comparative example, A is a scanning electron microscope image before the thermal shock resistance test of the copper-plated polyimide fiber prepared in the comparative example, and B is a scanning electron microscope image after the thermal shock resistance test of the copper-plated polyimide fiber prepared in the comparative example. As can be seen from fig. 1: the copper-plated polyimide fiber has poor thermal shock resistance and serious shedding of a metal copper plating layer.
Example 1
Step A: treating the polyimide fiber (40g) in a potassium hydroxide solution (5L,2mol/L) at 50 ℃ for 10min, and cleaning the potassium hydroxide with deionized water to obtain the polyimide fiber with the surface containing potassium carboxylate.
And B: and D, soaking the fiber obtained in the step A into a DMF (dimethyl formamide) solution (5L,0.5mol/L) containing the structure of the formula 102 at 60 ℃, and cleaning the fiber with deionized water after 5min to obtain the polyimide fiber with the surface bonded type 102 structure.
And C: and D, soaking the fiber obtained in the step B into a copper sulfate aqueous solution (4L,0.3mol/L) at the temperature of 20 ℃, and cleaning the fiber with deionized water after 3min to obtain the polyimide fiber with the surface complexed with copper ions.
Step D: and (3) immersing the fiber obtained in the step (C) into a sodium hypophosphite aqueous solution (4L,0.1mol/L) at the temperature of 20 ℃ for chemical reduction for 5min, and then cleaning the fiber by using deionized water to obtain the polyimide fiber with the surface containing ultrathin metal copper.
Step E: and D, soaking the fiber obtained in the step D into a chemical copper plating solution (5L, 15g/L of copper sulfate, 40g/L of potassium sodium tartrate, 8g/L of disodium ethylene diamine tetraacetate, 30mL/L of methanol and 20mL/L of 35-40% formaldehyde) at the temperature of 20 ℃ for 8min, cleaning with deionized water, and drying to obtain the copper-plated polyimide fiber.
Referring to fig. 2, fig. 2 is a thermal shock resistance test chart of the copper-plated polyimide fiber prepared in example 1 of the present invention, wherein C is a scanning electron microscope image of the copper-plated polyimide fiber prepared in example 1 before thermal shock resistance; d is a scanning electron microscope image of the copper-plated polyimide fiber prepared in example 1 after being subjected to thermal shock resistance after being cycled for 10 times at-180-200 ℃. As can be seen from fig. 2: the copper-plated polyimide fiber prepared by the method disclosed by the invention does not have metal falling off after being circulated for 10 times at the temperature of-180-200 ℃, and has higher thermal shock resistance.
Example 2
Step A: the same as in example 1.
And B: and D, soaking the fiber obtained in the step A into a DMF (4L,0.5mol/L) solution containing the structure of the formula 104 at 60 ℃, and cleaning the fiber with deionized water after 5min to obtain the polyimide fiber with the surface bonded structure of the formula 104.
And C: the same as in example 1.
Step D: the same as in example 1.
Step E: the same as in example 1.
Example 3
Step A: treating the polyimide fiber (4g) in a potassium hydroxide solution (0.5L,2mol/L) at 50 ℃ for 10min, and cleaning the potassium hydroxide by using deionized water to obtain the polyimide fiber with the surface containing potassium carboxylate.
And B: and D, soaking the fiber obtained in the step A into a DMF (0.4L,0.5mol/L) solution containing the structure of the formula 102 at 60 ℃, and cleaning the fiber with deionized water after 5min to obtain the polyimide fiber with the surface bonded type 102 structure.
And C: and D, soaking the fiber obtained in the step B into a silver nitrate aqueous solution (0.4L,0.3mol/L) at the temperature of 20 ℃, and cleaning the fiber with deionized water after 3min to obtain the polyimide fiber with the surface complexed with silver ions.
Step D: and (3) immersing the fiber obtained in the step (C) into a sodium hypophosphite aqueous solution (0.4L,0.1mol/L) at the temperature of 20 ℃ for chemical reduction for 5min, and then cleaning the fiber by using deionized water to obtain the polyimide fiber with the surface containing the ultrathin metal silver.
Step E: and D, immersing the fiber obtained in the step D into a chemical silver plating solution (0.5L, 10g/L of silver nitrate, 12g/L of ethylene diamine tetraacetic acid, 40mL/L of methanol and 8g/L of glucose) at the temperature of 20 ℃ for 8min, washing the fiber with deionized water, and drying the fiber to obtain the silver-plated polyimide fiber.
Referring to fig. 3, fig. 3 is a thermal shock resistance test chart of the silver-plated polyimide fiber prepared in example 3 of the present invention, wherein E is a scanning electron microscope image of the silver-plated polyimide fiber prepared in example 3 before thermal shock resistance; f is the scanning electron microscope image of the silver-plated polyimide fiber prepared in example 3 after 10 times of thermal shock resistance after circulation at-180 ℃ to 200 ℃. As can be seen from fig. 3: the silver-plated polyimide fiber prepared by the invention has no metal falling off after 10 times of circulation at-180-200 ℃, and has higher thermal shock resistance.
Example 4
Step A: the same as in example 3.
And B: and D, soaking the fiber obtained in the step A into a DMF (0.4L,0.5mol/L) solution containing the structure of the formula 104 at 60 ℃, and cleaning the fiber with deionized water after 5min to obtain the polyimide fiber with the surface bonded with the structure of the formula 104.
And C: the same as in example 3.
Step D: the same as in example 3.
Step E: the same as in example 3.
Example 5
Step A: treating the polyimide fiber (40g) in a potassium hydroxide solution (5L,2mol/L) at 50 ℃ for 10min, and cleaning the potassium hydroxide with deionized water to obtain the polyimide fiber with the surface containing potassium carboxylate.
And B: and D, soaking the fiber obtained in the step A into a DMF (4L,0.5mol/L) solution containing the structure of the formula 102 at 60 ℃, and cleaning the fiber with deionized water after 5min to obtain the polyimide fiber with the surface bonded type 102 structure.
And C: and D, soaking the fiber obtained in the step B into a nickel sulfate aqueous solution (4L,0.5mol/L) at the temperature of 20 ℃, and cleaning the fiber with deionized water after 3min to obtain the polyimide fiber with the surface complexed with nickel ions.
Step D: and (3) immersing the fiber obtained in the step (C) into a sodium hypophosphite aqueous solution (4L,0.1mol/L) at 60 ℃ for chemical reduction for 5min, and then cleaning the fiber by using deionized water to obtain the polyimide fiber with the surface containing the ultrathin metal nickel.
Step E: and D, soaking the fiber obtained in the step D into a chemical nickel plating solution (5L, 20g/L of nickel sulfate, 15g/L of trisodium citrate dihydrate, 20g/L of ammonium chloride and 15g/L of sodium hypophosphite, adjusting the pH value to 9-10 by using sodium hydroxide) at the temperature of 20 ℃ for 10min, washing the fiber by using deionized water, and drying the fiber to obtain the nickel-plated polyimide fiber.
Referring to fig. 4, fig. 4 is a thermal shock resistance test chart of the nickel-plated polyimide fiber prepared in example 5 of the invention, wherein G is a scanning electron microscope image of the nickel-plated polyimide fiber prepared in example 5 before thermal shock resistance; and H is a scanning electron microscope image of the nickel-plated polyimide fiber prepared in example 5 after being subjected to thermal shock resistance after being cycled for 10 times at-180-200 ℃. As can be seen from fig. 4: the nickel-plated polyimide fiber prepared by the invention has no metal falling off after 10 times of circulation at-180-200 ℃, and has higher thermal shock resistance.
Example 6
Step A: the same as in example 5.
And B: and D, soaking the fiber obtained in the step A into a DMF (4L,0.5mol/L) solution containing the structure of the formula 104 at 60 ℃, and cleaning the fiber with deionized water after 5min to obtain the polyimide fiber with the surface bonded structure of the formula 104.
And C: the same as in example 5.
Step D: the same as in example 5.
Step E: the same as in example 5.
The conductivity test of the thermal shock resistant conductive polyimide fibers prepared in the above examples 1 to 6 was carried out, and the results are shown in table 1:
TABLE 1 conductivity results for thermal shock resistant conductive polyimide fibers prepared in examples 1-6
Figure BDA0002095200390000121
From the above embodiments, the invention provides a thermal shock resistant conductive polyimide fiber, which comprises a modified polyimide fiber; and a metal transition layer and a metal coating layer which are sequentially compounded on the surface of the modified polyimide fiber; the surface of the modified polyimide fiber is modified by a pyridine derivative or a quinoline derivative; the metal in the metal transition layer is selected from copper, nickel or silver; the metal in the metal plating layer is selected from copper, nickel or silver. The fiber provided by the invention takes the polyimide fiber as a base fiber, the surface of the polyimide fiber is modified by the pyridine derivative or the quinoline derivative, a transition layer containing the pyridine derivative or the quinoline derivative is introduced between the surface of the polyimide fiber and a plating layer metal through a covalent bond and a coordination bond to play a role of soft connection, and the bonding performance of the fiber and the metal is improved by utilizing the strong action force of the pyridine, an amido bond and the metal, so that the thermal shock resistance of the conductive fiber is improved. The fibers also have high electrical conductivity. The experimental results show that: the inventionThe conductivity of the provided fiber is 1.15 × 104～5.0×104S/cm; no metal falling off after 10 times of circulation at minus 180 ℃ to 200 ℃.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A thermal shock resistant conductive polyimide fiber comprises a modified polyimide fiber;
and a metal transition layer and a metal coating layer which are sequentially compounded on the surface of the modified polyimide fiber;
the surface of the modified polyimide fiber is modified by a pyridine derivative or a quinoline derivative;
the metal in the metal transition layer is selected from copper, nickel or silver;
the metal in the metal plating layer is selected from copper, nickel or silver;
the pyridine derivative is selected from formula 101, formula 102, formula 103 or formula 104; the quinoline derivative is selected from formula 105;
Figure FDA0002444062220000011
the surface of the modified polyimide fiber and the metal of the coating are introduced into a transition layer containing pyridine derivatives or quinoline derivatives through covalent bonds and coordination bonds to play a role of soft connection, and strong action force exists between the pyridine derivatives and amide bonds and the metal.
2. The thermal shock resistant conductive polyimide fiber as claimed in claim 1, wherein the metal in the metal transition layer and the metal plating layer is the same metal.
3. A preparation method of the thermal shock resistant conductive polyimide fiber as claimed in any one of claims 1 to 2, comprising the following steps:
performing alkaline treatment on the polyimide fiber, and cleaning to obtain the polyimide fiber with the surface containing carboxylate;
putting the polyimide fiber with the carboxylate on the surface into a solution of a pyridine derivative or a quinoline derivative for reaction, and cleaning to obtain the polyimide fiber with the surface containing the pyridine derivative or the quinoline derivative;
placing the polyimide fiber with the surface containing the pyridine derivative or the quinoline derivative in a soluble metal salt aqueous solution to complex metal ions to obtain the polyimide fiber with the surface containing the metal ions;
reducing and cleaning the polyimide fiber with the surface containing metal ions to obtain the polyimide fiber with the surface compounded with the metal transition layer;
and placing the polyimide fiber with the surface compounded with the metal transition layer into a plating solution for chemical plating to obtain the thermal shock resistant conductive polyimide fiber.
4. The production method according to claim 3, wherein the substance used for the alkaline treatment is a potassium hydroxide solution; the temperature of the alkaline treatment is 20-60 ℃; the time of alkaline treatment is 10-30 min.
5. The preparation method according to claim 3, wherein the reaction temperature is 60-100 ℃; the reaction time is 5-30 min.
6. The method of claim 3, wherein the aqueous solution of the soluble metal salt is selected from one or more of copper sulfate, copper nitrate, silver nitrate, nickel nitrate, and nickel sulfate;
the concentration of the soluble metal salt water solution is 0.1-0.6 mol/L;
the complexing temperature is 20-30 ℃; the complexing time is 5-30 min.
7. The preparation method according to claim 3, wherein the reducing agent used for the reduction is selected from any one or more of stannous chloride, dimethylamino borane, sodium hypophosphite, hydrazine hydrate, sodium ascorbate, formaldehyde and formic acid;
the reduction temperature is 10-50 ℃; the reduction time is 1-30 min.
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CN101660264A (en) * 2009-09-11 2010-03-03 北京化工大学 Method for preparing polyimide/silver composite conductive fiber
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