CN110144729B - Conductive gold-coated polyimide fiber and preparation method thereof - Google Patents
Conductive gold-coated polyimide fiber and preparation method thereof Download PDFInfo
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Abstract
The invention provides a conductive gold-coated polyimide fiber and a preparation method thereof, the conductive gold-coated polyimide fiber comprises a modified polyimide fiber, and a palladium metal particle layer and a gold layer which are sequentially compounded on the surface of the modified polyimide fiber, the modified polyimide fiber is a polyimide fiber with carboxylate on the surface or a polyimide fiber with pyridine derivatives or quinoline derivatives on the surface through ester bond, the fiber takes the polyimide fiber as a base fiber, and the modification is carried out by adopting carboxylate or ester bond pyridine derivatives or quinoline derivatives, so that the thermal shock resistance of the gold-coated fiber is improved, the conductivity is higher, the corrosion resistance and the oxidation resistance are excellent, the application temperature range is wide, the thermal shock resistance of the fiber is good at minus 180-200 ℃, the metal falling does not occur after 10 times of circulation, and the conductivity is 4.53 × 103～1.87×104S/cm; the conductivity and the mechanical properties of the fiber can be maintained in corrosive and oxidative environments.
Description
Technical Field
The invention belongs to the technical field of polyimide, and particularly relates to a conductive gold-coated polyimide fiber and a preparation method thereof.
Background
At present, the electromagnetic shielding device is an electronic age, high-energy rays applied to multiple fields of medicine, military and electronics and electromagnetic radiation brought by electronic equipment in daily life bring inevitable harm to human health, and various electromagnetic shielding products are produced. Conductive fiber textiles are increasingly used as shielding raw materials. As high performance organic fibers, copper, nickel and silver plated polyimide fibers have been developed (CN101446037B, CN101775670B, CN107313249A, CN106702356A) that can meet the requirements of shielding performance, but have limited use in some corrosive environments.
The gold plating surface treatment technology has good corrosion resistance and oxidation resistance, so the development of gold plating polyimide fibers has good application prospect, but no related report of polyimide fiber gold plating exists at present.
Disclosure of Invention
In view of the above, the present invention aims to provide a conductive gold-coated polyimide fiber and a preparation method thereof, wherein the conductive gold-coated polyimide fiber has high thermal shock resistance and corrosion resistance.
The invention provides a conductive gold-coated polyimide fiber, which is characterized by comprising a modified polyimide fiber;
and a palladium metal particle layer and a gold layer which are sequentially compounded on the surface of the modified polyimide fiber;
the modified polyimide fiber is a polyimide fiber with carboxylate on the surface or a polyimide fiber with pyridine derivatives or quinoline derivatives on the surface and bonded through ester bonds.
Preferably, the polyimide fiber having a surface containing a pyridine derivative or a quinoline derivative bonded through an ester bond is produced by the following method:
the polyimide fiber containing carboxylate on the surface is put into solution of pyridine derivative or quinoline derivative for reaction and is cleaned to obtain the polyimide fiber.
Preferably, the pyridine derivative is selected from formula 101, formula 102, formula 103, or formula 104; the quinoline derivative is selected from formula 105;
the invention provides a preparation method of a conductive gold-coated polyimide fiber, which comprises the following steps:
step A: performing alkaline treatment on the polyimide fiber, and cleaning to obtain the polyimide fiber with the surface containing carboxylate;
and B: b, placing the fiber obtained in the step A in a solution of a pyridine derivative or a quinoline derivative for reaction, and cleaning to obtain an ester bond polyimide fiber with the surface containing the pyridine derivative or the quinoline derivative;
and C: placing the fiber obtained in the step A or the step B in a palladium salt solution for palladium ion exchange or complexation, and cleaning to obtain a polyimide fiber with a palladium ion-containing surface;
step D: reducing and cleaning the polyimide fiber with the palladium ion-containing surface to obtain the polyimide fiber with the palladium metal particle layer compounded on the surface;
step E: and chemically plating gold on the polyimide fiber with the surface compounded with the palladium metal particle layer, and cleaning to obtain the conductive gold-coated polyimide fiber.
Preferably, the alkali treatment is with potassium hydroxide; the temperature of the alkali treatment is 20-60 ℃; the alkali treatment time is 10-30 min.
Preferably, the solvent in the solution of the pyridine derivative or quinoline derivative is 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 0.5-2 mol/L. A
Preferably, the reaction temperature in the step B is 60-100 ℃; the reaction time is 5-30 min.
Preferably, the palladium salt in step C is selected from palladium chloride, palladium acetate, palladium trifluoroacetate, palladium trifluoromethanesulfonate or palladium sulfate.
Preferably, the temperature of the exchange or complexation in the step C is 20-60 ℃ and the time is 5-30 min.
Preferably, the reducing agent used in the reduction in the step D is one or more selected from 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 conductive gold-coated polyimide fiber, which comprises a modified polyimide fiber; and a palladium metal particle layer and a gold layer which are sequentially compounded on the surface of the modified polyimide fiber; the modified polyimide fiber is a polyimide fiber with carboxylate on the surface or a polyimide fiber with pyridine derivatives or quinoline derivatives on the surface and bonded through ester bonds. The fiber provided by the invention takes polyimide fiber as base fiber, and carboxylate is adoptedOr ester bond pyridine derivative or quinoline derivative, so that the thermal shock resistance of the gold-plated fiber is improved, the conductivity is higher, the gold-plated fiber also has excellent corrosion resistance and oxidation resistance and a wide use temperature range, experimental results show that the thermal shock resistance of the conductive gold-coated polyimide fiber is good at minus 180-200 ℃, no metal falls off after 10 times of circulation, and the conductivity is 4.53 × 103～1.87×104S/cm; the conductivity of the conductive gold-coated polyimide fiber in acid, alkali and atomic oxygen environments is basically maintained; the mechanical property attenuation of the conductive gold-coated polyimide fiber subjected to carboxylate modification on the surface of the fibril is obvious, particularly in an alkaline environment and an atomic oxygen environment; the conductivity and the fiber mechanical property of the gold-plated polyimide fiber with the surface of the fibril modified by the pyridine derivative or the quinoline derivative in a corrosive environment and an oxidizing environment can be maintained.
Drawings
FIG. 1 is a thermal shock resistance test chart of gold-coated polyimide fibers prepared in example 1 of the present invention;
FIG. 2 is a thermal shock resistance test chart of the gold-coated polyimide fiber prepared in example 4 of the present invention.
Detailed Description
The invention provides a conductive gold-coated polyimide fiber, which comprises a modified polyimide fiber;
and a palladium metal particle layer and a gold layer which are sequentially compounded on the surface of the modified polyimide fiber;
the modified polyimide fiber is a polyimide fiber with carboxylate on the surface or a polyimide fiber with pyridine derivatives or quinoline derivatives on the surface and bonded through ester bonds.
The fiber provided by the invention takes the polyimide fiber as the base fiber, and the thermal shock resistance of the gold-plated fiber is improved by adopting carboxylate or ester bond pyridine derivative or quinoline derivative for modification. The conductivity is high, the corrosion resistance and the oxidation resistance are excellent, and the using temperature range is wide.
The conductive gold-coated polyimide fiber provided by the invention comprises a modified polyimide fiber; the modified polyimide fiber is a polyimide fiber with carboxylate on the surface or a polyimide fiber with pyridine derivatives or quinoline derivatives on the surface and bonded through ester bonds. 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 carboxylic acid salt is preferably potassium carboxylate; the pyridine derivative is selected from formula 101, formula 102, formula 103 or formula 104; the quinoline derivative is selected from formula 105;
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.
The conductive gold-coated polyimide fiber provided by the invention further comprises a palladium metal particle layer and a gold layer which are sequentially compounded on the surface of the modified polyimide fiber. In the invention, the thickness of the gold layer is preferably 0.3-1.0 μm.
The invention provides a preparation method of a conductive gold-coated polyimide fiber, which comprises the following steps:
step A: performing alkaline treatment on the polyimide fiber, and cleaning to obtain the polyimide fiber with the surface containing carboxylate;
and B: b, placing the fiber obtained in the step A in a solution of a pyridine derivative or a quinoline derivative for reaction, and cleaning to obtain an ester bond polyimide fiber with the surface containing the pyridine derivative or the quinoline derivative;
and C: placing the fiber obtained in the step A or the step B in a palladium salt solution for palladium ion exchange or complexation, and cleaning to obtain a polyimide fiber with a palladium ion-containing surface;
step D: reducing and cleaning the polyimide fiber with the palladium ion-containing surface to obtain the polyimide fiber with the palladium metal particle layer compounded on the surface;
step E: and chemically plating gold on the polyimide fiber with the surface compounded with the palladium metal particle layer, and cleaning to obtain the conductive gold-coated polyimide fiber.
The polyimide fiber is subjected to alkaline treatment and cleaning 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.
And B, placing the fiber obtained in the step A in a solution of a pyridine derivative or a quinoline derivative for reaction, and cleaning to obtain the polyimide fiber with the ester bond and the surface containing the pyridine derivative or the quinoline derivative. 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, the reaction product is preferably washed by deionized water, and the washing is thorough.
The method comprises the steps of placing the fiber obtained in the step A or the step B in a palladium salt solution for palladium ion exchange or complexation, and cleaning to obtain the polyimide fiber with the surface containing palladium ions. In the present invention, the palladium salt is selected from palladium chloride, palladium acetate, palladium trifluoroacetate, palladium trifluoromethanesulfonate or palladium sulfate. The concentration of the palladium salt solution is preferably 1-5 g/L. The temperature of the exchange or the complexation is 20-60 ℃, and the time is 5-30 min. The exchanged or complexed fibers are preferably washed with deionized water and cleaned.
The polyimide fiber with the palladium metal particle layer compounded on the surface is obtained by reducing and cleaning the polyimide fiber with the palladium ion contained on the surface. In the invention, the reducing agent used for the reduction is selected from 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 0.01mol/L to 2 mol/L. The reduction temperature is preferably 10-50 ℃; the reduction time is 1-30 min.
The polyimide fiber with the surface compounded with the palladium metal particle layer is subjected to chemical gold plating and is cleaned, and the conductive gold-coated polyimide fiber is obtained. In the invention, the main salt adopted by the chemical gold plating is selected from sodium chloroaurate, potassium chloroaurate and chloroauric acid, and the concentration of a gold salt solution for the chemical gold plating is 0.2-2.0 g/L in terms of gold ions. The main complexing agent for chemical gold plating is any one or the combination of more than two of thiourea, urea, ammonia water, pyridine, 4-dimethylamino pyridine, 1-methylimidazole, ethylene diamine tetraacetic acid, ethylenediamine, sodium sulfite and potassium sulfite, and the concentration of the main complexing agent is 0.1 mol/L-0.5 mol/L; the auxiliary complexing agent for chemical gold plating is any one of citric acid, tartaric acid, lactic acid, malic acid, gluconic acid, acetic acid, propionic acid, glycine, aspartic acid and sodium salt, potassium salt and ammonium salt thereof, and the concentration of the auxiliary complexing agent is 0.1-1.0 mol/L; the reducing agent for chemical gold plating is any one or the combination of more than two of dimethylamino borane, sodium hypophosphite, hydrazine, sodium ascorbate and formic acid, and the concentration of the reducing agent is 0.1 mol/L-1.0 mol/L; the pH buffer for electroless gold plating is selected from NaH2PO4,KH2PO4,Na2HPO4And K2HPO4Any one or more of them, and the concentration is 0.1 mol/L-0.5 mol/L. The pH value of the plating solution is 3-9 during electroless gold plating. The temperature of the electroless gold plating is preferably 20-70 ℃.
The method provided by the invention has wide application range, is suitable for polyimide fibers of various systems, and is also suitable for continuous production.
The conductive gold-coated polyimide fiber prepared by the invention has low loss rate of mechanical properties, good conductive performance and electromagnetic shielding performance and wide use temperature range, and can be used as an antistatic and shielding material to be applied in corrosive and oxidative environments.
To further illustrate the present invention, the following will describe in detail a conductive gold-coated polyimide fiber and a method for preparing the same in connection with examples, which should not be construed as limiting the scope of the present invention.
Preparatory example 1
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 a saturated aqueous solution of sodium hydrogencarbonate (100.0mL), the organic phase was dried over anhydrous sodium sulfate, the drying agent was filtered off, methylene chloride was distilled off, and vacuum drying was carried out to obtain a reddish solid (76.8g, yield: 90%) which was a pyridine derivative represented by the formula 102.1H 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
The preparation process is the same as that of preparation example 1, using 3-aminopyridine as a reaction raw material, and the product is a white solid, namely, a pyridine derivative represented by the structure of formula 103, with the yield: 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
Reacting 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, methylene chloride was distilled off, and vacuum drying was carried out to give a white solid (77.6g, yield: 91%) which is a pyridine derivative represented by the formula 104.1H 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
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 a saturated aqueous solution of sodium bicarbonate (150.0mL), the organic phase was dried over anhydrous sodium sulfate, the drying agent was filtered off, after methylene chloride was distilled off, petroleum ether (200.0mL) was added, and after stirring for 30min, filtration and vacuum drying were carried out to obtain a reddish solid (107.0g, yield: 97%) which was the quinoline derivative having the structure represented by formula 105.1H 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)。
Example 1
Step A: treating the polyimide fiber in 2mol/L potassium hydroxide solution at 50 ℃ for 10min, and cleaning the potassium hydroxide with deionized water to obtain the polyimide fiber with the surface containing potassium carboxylate.
And C: and D, soaking the fiber obtained in the step A into a dimethyl formamide solution (3g/L) of palladium chloride at the temperature of 20 ℃, and cleaning the fiber with deionized water after 5min to obtain the polyimide fiber with the surface complexed with palladium ions.
Step D: and (3) immersing the fiber obtained in the step (C) into a dimethylamino borane solution (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 palladium metal layer.
Step E: immersing the fiber obtained in the step D into electroless gold plating solution (0.5 g/L of sodium chloroaurate, 20g/L of acetic acid, 8g/L of disodium ethylenediamine tetraacetic acid, 10mL/L of formic acid, 30g/L of trisodium citrate, K) at the temperature of 50 DEG C2HPO430g/L, pH 5-6) for 30min, cleaning with deionized water, and drying to obtain the gold-coated polyimide fiber.
Referring to fig. 1, fig. 1 is a thermal shock resistance test chart of gold-coated polyimide fibers prepared in example 1 of the present invention; wherein A is a scanning electron microscope image of the gold-coated polyimide fiber before thermal shock resistance test; and B is a scanning electron microscope image after the thermal shock resistance test of the gold-coated polyimide fiber. As seen from fig. 1: the conductive gold-coated 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 2
Step A: the same as in example 1.
And B: and D, soaking the fiber obtained in the step A into a DMF (0.5mol/L) solution containing the structure of the formula 101 at the temperature of 80 ℃, and cleaning the fiber by using deionized water after 5min to obtain the polyimide fiber with the surface bonded structure of the formula 101.
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: the same as in example 1.
And B: and D, soaking the fiber obtained in the step A into a DMF (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: the same as in example 1.
Step D: the same as in example 1.
Step E: the same as in example 1.
Example 4
Step A: the same as in example 1.
And B: and D, soaking the fiber obtained in the step A into a DMF (0.5mol/L) solution containing the structure of the formula 103 at 60 ℃, and cleaning the fiber with deionized water after 5min to obtain the polyimide fiber with the surface bonded structure of the formula 103.
And C: the same as in example 1.
Step D: the same as in example 1.
Step E: the same as in example 1.
FIG. 2 is a thermal shock resistance test chart of the gold-coated polyimide fiber prepared in example 4 of the present invention, wherein A is a scanning electron microscope image of the gold-coated polyimide fiber before the thermal shock resistance test; b is a scanning electron microscope image of the thermal shock resistance test of the gold-coated polyimide fiber after 10 times of circulation at-180 to 200 ℃. As can be seen from fig. 2: the conductive gold-coated 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 5
Step A: the same as in example 1.
And B: and D, soaking the fiber obtained in the step A into a DMF (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 1.
Step D: the same as in example 1.
Step E: the same as in example 1.
Example 6
Step A: the same as in example 1.
And B: and D, soaking the fiber obtained in the step A into a DMF (0.5mol/L) solution containing the structure of the formula 105 at the temperature of 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 105.
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 7
Step A: the same as in example 1.
And B: and D, soaking the fiber obtained in the step A into a DMF (0.5mol/L) solution containing the structure of the formula 103 at 60 ℃, and cleaning the fiber with deionized water after 5min to obtain the polyimide fiber with the surface bonded structure of the formula 103.
And C: the same as in example 1.
Step D: the same as in example 1.
Step E: immersing the fiber obtained in the step D into electroless gold plating solution (0.5 g/L of sodium chloroaurate, 25g/L of urea, 8g/L of sodium sulfite, 30g/L of trisodium citrate, 5g/L of sodium ascorbate, K) at the temperature of 20 DEG C2HPO430g/L, pH 8-9) for 30min, cleaning with deionized water, and drying to obtain the gold-coated polyimide fiber.
Example 8
Step A: the same as in example 1.
And B: the same as in example 7.
And C: the same as in example 1.
Step D: the same as in example 1.
Step E: d, immersing the fiber obtained in the step D into electroless gold plating solution (0.5 g/L of sodium chloroaurate, 8g/L of sodium sulfite, 30g/L of trisodium citrate, 12g/L of sodium hypophosphite, K) at the temperature of 20 DEG C2HPO430g/L, pH 8-9) for 30min, washing with deionized water, and drying to obtain the gold-plated polyimide fiber.
The conductivity tests of the gold-plated polyimide fibers prepared in examples 1-2, 4 and 6-8 above were conducted according to the present invention, and the results are shown in Table 1:
TABLE 1 conductivity results for gold plated polyimide fibers prepared in examples 1-2, 4 and 6-8
The gold-plated polyimide fibers prepared in examples 1, 4, 7 and 8 above were subjected to acid, alkali and atomic oxygen resistance tests, as shown in tables 2 to 4. The results show that the conductivity of the gold-plated polyimide fiber which is not modified by the pyridine derivative or the quinoline derivative can be maintained in a corrosive environment and an oxidizing environment, but the mechanical property attenuation is obvious, particularly in an alkaline environment and an oxidizing environment. This is mainly due to the loose structure of the gold plating layer and the unsmooth surface caused by the non-uniformity of the palladium activation layer, as shown in fig. 1. The loose structure can cause the entry of acid, alkali and oxygen atoms, thereby corroding the fiber and reducing the mechanical property of the fiber; the conductivity and the fiber mechanical property of the gold-plated polyimide fiber modified by the pyridine derivative or the quinoline derivative in a corrosive environment and an oxidative environment can be maintained, and the gold plating layer of the fiber has a compact structure and a smooth surface, as shown in figure 2.
Table 2 results of acid corrosion resistance of gold plated polyimide fibers prepared in examples 1, 4, 7 and 8
Note: a is newly prepared gold-plated polyimide fiber; b is gold-plated polyimide fiber which is soaked in 1mol/L hydrochloric acid for 100 hours at the temperature of 80 DEG C
Table 3 results of alkali corrosion resistance of gold plated polyimide fibers prepared in examples 1, 4, 7 and 8
Note: a is newly prepared gold-plated polyimide fiber; b is gold plated polyimide fiber after soaking in 2mol/L aqueous sodium hydroxide solution at 80 ℃ for 100 hours Table 4 results for atomic oxygen corrosion resistance of gold plated polyimide fibers prepared in examples 1, 4, 7 and 8
Note that A is newly prepared gold-plated polyimide fiber, and B is 3.2 × 1020atoms/cm2Gold-plated polyimide fiber treated by atomic oxygen in dosage
From the above embodiments, the present invention provides a conductive gold-coated polyimide fiber, including a modified polyimide fiber; and a palladium metal particle layer and a gold layer which are sequentially compounded on the surface of the modified polyimide fiber; the modified polyimide fiber is a polyimide fiber with carboxylate on the surface or a surface bonded by ester bondThe fiber provided by the invention takes the polyimide fiber as a base fiber, and is modified by adopting carboxylate or ester bond bonding of the pyridine derivative or the quinoline derivative, so that the thermal shock resistance of the gold-plated fiber is improved, the conductivity is higher, the gold-plated fiber also has excellent corrosion resistance and oxidation resistance and a wide use temperature range, and experimental results show that the conductive gold-coated polyimide fiber has good thermal shock resistance at the temperature of-180-200 ℃, does not have metal falling after 10 times of circulation, and the conductivity is 4.53 × 103～1.87×104S/cm, the conductivity of the conductive gold-coated polyimide fiber in acid, alkali and atomic oxygen environments is basically maintained, but the mechanical property attenuation of the fiber which is not modified by pyridine derivatives or quinoline derivatives is obvious, particularly in alkaline environments and atomic oxygen environments, the conductivity and the mechanical property of the gold-plated polyimide fiber modified by pyridine derivatives or quinoline derivatives in corrosive environments and oxidizing environments can be maintained, the strength of the gold-plated polyimide fiber before 1mol/L hydrochloric acid soaking at 80 ℃ is 12.14-12.51 cN/dtex, the modulus after 100h soaking is 11.49-12.55 cN/dtex, the modulus before acid soaking is 597.43-606.47 cN/dtex, the modulus after 100h acid soaking is 584.01-601.38 cN/dtex, the elongation at break before acid soaking is 3.74-3.84%, the elongation after acid soaking is 3.86-4.16%, and the conductivity before acid soaking is 4.53 × 103～1.87×104S/cm, conductivity after acid soaking for 100h is 4.60 × 103～1.90×104The S/cm. gold-plated polyimide fiber has a strength of 5.52-12.60 cN/dtex after being soaked in 2mol/L sodium hydroxide aqueous solution for 100 hours at 80 ℃, a modulus of 242.61-606.13 cN/dtex, an elongation at break of 3.77-5.21% and an electric conductivity of 4.50 × 103～1.81×104S/cm. at 3.2 × 1020atoms/cm2The strength of the gold-plated polyimide fiber after the atomic oxygen dose treatment is 6.35-12.41 cN/dtex, the modulus is 418.74-602.87 cN/dtex, the elongation at break is 3.70-4.74%, and the conductivity is 4.55 × 103～1.84×104S/cm。
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 (8)
1. A conductive gold-coated polyimide fiber is characterized by comprising a modified polyimide fiber;
and a palladium metal particle layer and a gold layer which are sequentially compounded on the surface of the modified polyimide fiber;
the modified polyimide fiber is a polyimide fiber which is bonded through ester bonds and contains pyridine derivatives or quinoline derivatives on the surface; the polyimide fiber with the surface containing pyridine derivatives or quinoline derivatives and bonded by ester bonds is prepared by the following method: putting the polyimide fiber with the surface containing carboxylate into a solution of pyridine derivative or quinoline derivative for reaction, and cleaning to obtain the polyimide fiber;
the pyridine derivative is selected from formula 101, formula 102, formula 103 or formula 104; the quinoline derivative is selected from formula 105;
2. a method for preparing the conductive gold-coated polyimide fiber of claim 1, comprising the steps of:
step A: performing alkaline treatment on the polyimide fiber, and cleaning to obtain the polyimide fiber with the surface containing carboxylate;
and B: b, placing the fiber obtained in the step A in a solution of a pyridine derivative or a quinoline derivative for reaction, and cleaning to obtain an ester bond polyimide fiber with the surface containing the pyridine derivative or the quinoline derivative;
and C: placing the fiber obtained in the step B in a palladium salt solution for carrying out palladium ion complexation, and cleaning to obtain a polyimide fiber with a palladium ion-containing surface;
step D: reducing and cleaning the polyimide fiber with the palladium ion-containing surface to obtain the polyimide fiber with the palladium metal particle layer compounded on the surface;
step E: and chemically plating gold on the polyimide fiber with the surface compounded with the palladium metal particle layer, and cleaning to obtain the conductive gold-coated polyimide fiber.
3. The production method according to claim 2, wherein the alkali treatment is performed using potassium hydroxide; the temperature of the alkali treatment is 20-60 ℃; the alkali treatment time is 10-30 min.
4. The method according to claim 2, wherein the solvent in the solution of the pyridine derivative or quinoline derivative is selected from the group consisting of water, dimethylformamide, dimethylacetamide andN-one or more of methyl pyrrolidone;
the concentration of the solution of the pyridine derivative or the quinoline derivative is 0.5-2 mol/L.
5. The preparation method according to claim 2, wherein the temperature of the reaction in the step B is 60-100 ℃; the reaction time is 5-30 min.
6. The method according to claim 2, wherein the palladium salt in step C is selected from palladium chloride, palladium acetate, palladium trifluoroacetate, palladium trifluoromethanesulfonate and palladium sulfate.
7. The preparation method according to claim 2, wherein the temperature of the complexation in the step C is 20-60 ℃ and the time is 5-30 min.
8. The preparation method according to claim 2, wherein the reducing agent used in the reduction in the step D is one or more selected from 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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