CN110144729A - A kind of conductive gold cladding polyimide fiber and preparation method thereof - Google Patents
A kind of conductive gold cladding polyimide fiber and preparation method thereof Download PDFInfo
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- CN110144729A CN110144729A CN201910516434.XA CN201910516434A CN110144729A CN 110144729 A CN110144729 A CN 110144729A CN 201910516434 A CN201910516434 A CN 201910516434A CN 110144729 A CN110144729 A CN 110144729A
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- 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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- 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
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- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
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- 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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Abstract
The present invention provides a kind of conductive gold cladding polyimide fibers and preparation method thereof, and it includes modified polyimide fiber that conductive gold, which coats polyimide fiber,；And successively it is compounded in the palladium metal particle layer and layer gold of the modified polyimide fiber surface；Modified polyimide fiber is the polyimide fiber of surface carboxylate-containing or polyimide fiber of the surface containing pyridine derivate or quinoline by ester bond bonding.The fiber is modified, so that the thermal shock resistance of gold-plated fiber is improved using polyimide fiber as base fibre by using carboxylate or ester bond bonding pyridine derivate or quinoline.Conductivity is higher, and excellent anticorrosive and inoxidizability, use temperature range are wide.Fiber is good in -180 DEG C~200 DEG C thermal shock resistances, recycles 10 times and falls off without metal；Conductivity is 4.53 × 103~1.87 × 104S/cm；Conductivity and fibrous mechanical property in corrosive environment and oxidative environment can be kept.
Description
Technical field
The invention belongs to polyimides technical field more particularly to a kind of conductive gold cladding polyimide fiber and its preparations
Method.
Background technique
It is the electronic epoch now, applied to medicine, military, electronics multiple fields high-energy ray and is applied to daily life
Electromagnetic radiation brought by electronic equipment living brings inevitable injury to human health, various electromagnetic shielded products meet the tendency of and
It is raw.Conductive fiber textile is as shielding raw material using increasingly extensive.As high-performance organic fibre, copper facing, nickel plating and
Silver-plated polyimide fiber developed (CN101446037B, CN101775670B, CN107313249A,
CN106702356A), it can satisfy the requirement of shielding properties, but using limited in some corrosive environments.
Gold-plated surface processing technique has good corrosion-resistant and antioxygenic property, therefore, it is fine to develop gold-plated polyimides
Dimension has a good application prospect, and still, there is presently no the relevant reports that polyimide fiber is gold-plated.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of conductive gold cladding polyimide fiber and preparation method thereof,
Fiber thermal shock resistance with higher and corrosion resistance.
The present invention provides a kind of conductive golds to coat polyimide fiber, which is characterized in that including modified polyimide fibre
Dimension；
And successively it is compounded in the palladium metal particle layer and layer gold of the modified polyimide fiber surface；
The modified polyimide fiber is the polyimide fiber of surface carboxylate-containing or the surface by ester bond bonding
Polyimide fiber containing pyridine derivate or quinoline.
Preferably, it is described by ester bond be bonded polyimide fiber of the surface containing pyridine derivate or quinoline by
Following methods are made:
The polyimide fiber of surface carboxylate-containing is placed in the solution of pyridine derivate or quinoline and is reacted, clearly
It washes obtained.
Preferably, the pyridine derivate is selected from formula 101, formula 102, formula 103 or formula 104；The quinoline is selected from
Formula 105；
The present invention provides a kind of preparation methods of the cladding polyimide fiber of conductive gold described in above-mentioned technical proposal, including
Following steps:
Step A: carrying out basic treatment for polyimide fiber, and cleaning obtains the polyimide fiber of surface carboxylate-containing；
Step B: the obtained fiber of step A being placed in the solution of pyridine derivate or quinoline and is reacted, and cleaning obtains
Polyimide fiber of the surface containing pyridine derivate or quinoline being bonded to ester bond；
Step C: the obtained fiber of step A or step B is placed in palladium salt solution and carries out palladium ion exchange or complexing, clearly
It washes, obtains polyimide fiber of the surface containing palladium ion；
Step D: the polyimide fiber reduction by the surface containing palladium ion, cleaning obtain surface recombination palladium metal grain
The polyimide fiber of sublayer；
Step E: by the polyimide fiber chemical gilding of the surface recombination palladium metal particle layer, cleaning obtains conduction
Gold cladding polyimide fiber.
Preferably, the alkali process uses potassium hydroxide；The temperature of the alkali process is 20~60 DEG C；The alkali process
Time is 10~30min.
Preferably, the solvent in the solution of the pyridine derivate or quinoline is selected from water, dimethylformamide, two
One of methylacetamide and N-Methyl pyrrolidone are a variety of；
The concentration of the solution of the pyridine derivate or quinoline is 0.5~2mol/L.,
Preferably, the temperature reacted in the step B is 60~100 DEG C；The time of reaction is 5~30min.
Preferably, palladium salt is selected from palladium chloride, palladium acetate, palladium trifluoroacetate, trifluoromethanesulfonic acid palladium or sulfuric acid in the step C
Palladium.
Preferably, the temperature for exchanging or being complexed in the step C is 20~60 DEG C, and the time is 5~30min.
Preferably, restored in the step D use reducing agent be selected from stannous chloride, dimethylamino borine, sodium hypophosphite,
One of hydrazine hydrate, sodium ascorbate, formaldehyde and formic acid are a variety of；
The temperature of the reduction is 10~50 DEG C；The time of reduction is 1~30min.
The present invention provides a kind of conductive golds to coat polyimide fiber, including modified polyimide fiber；And it is successively multiple
Close the palladium metal particle layer and layer gold in the modified polyimide fiber surface；The modified polyimide fiber contains for surface
The polyimide fiber of carboxylate or the surface being bonded by ester bond are containing the polyimides of pyridine derivate or quinoline fibre
Dimension.Fiber provided by the invention using polyimide fiber as base fibre, by using carboxylate or ester bond bonding pyridine derivate or
Quinoline is modified, so that the thermal shock resistance of gold-plated fiber improves.Conductivity is higher, also has excellent corrosion resistance
It is wide with inoxidizability, use temperature range.The results showed that conductive gold coats polyimide fiber at -180 DEG C~200 DEG C
Thermal shock resistance it is good, circulation falls off for 10 times without metal；Conductivity is 4.53 × 103~1.87 × 104S/cm；Conductive gold packet
Conductivity of the polyimide fiber in acid, alkali and atomic oxygen environment is covered to keep substantially；Fibril surface carries out Carboxylate-modified
Conductive gold coats the decaying of polyimide fiber mechanical property obviously, especially in alkaline environment and atomic oxygen environment；Fibril table
The gold-plated polyimide fiber that face progress pyridine derivate or quinoline are modified is in corrosive environment and oxidative environment
Conductivity and fibrous mechanical property can keep.
Detailed description of the invention
Fig. 1 is the thermal shock resistance test chart of gold cladding polyimide fiber prepared by the embodiment of the present invention 1；
Fig. 2 is the thermal shock resistance test chart of gold cladding polyimide fiber prepared by the embodiment of the present invention 4.
Specific embodiment
The present invention provides a kind of conductive golds to coat polyimide fiber, including modified polyimide fiber；
And successively it is compounded in the palladium metal particle layer and layer gold of the modified polyimide fiber surface；
The modified polyimide fiber is the polyimide fiber of surface carboxylate-containing or the surface by ester bond bonding
Polyimide fiber containing pyridine derivate or quinoline.
Fiber provided by the invention is pyridine derived by using carboxylate or ester bond bonding using polyimide fiber as base fibre
Object or quinoline are modified, so that the thermal shock resistance of gold-plated fiber improves.Conductivity is higher, also has excellent corrosion resistant
Corrosion and inoxidizability, use temperature range are wide.
Conductive gold cladding polyimide fiber provided by the invention includes modified polyimide fiber；The modified polyamides is sub-
Amine fiber is the polyimide fiber of surface carboxylate-containing or contains pyridine derivate or quinoline derivatives by the surface that ester bond is bonded
The polyimide fiber of object.In the present invention, the polyimide fiber average diameter is 18um, line density 300D/0.1K.
In the present invention, the carboxylate is preferably carboxylic acid potassium；The pyridine derivate is selected from formula 101, formula 102, formula 103 or formula 104；
The quinoline is selected from formula 105；
In the present invention, the pyridine derivate of 102 structure of formula is preferably made according to the following steps:
2-aminopyridine, triethylamine and methylene chloride are mixed, the reaction of 2- chloracetyl chloride is added dropwise, obtains 102 structure of formula
Pyridine derivate.
The pyridine derivate of 103 structure of formula is preferably made according to the following steps:
3- aminopyridine, triethylamine and methylene chloride are mixed, the reaction of 2- chloracetyl chloride is added dropwise, obtains 103 structure of formula
Pyridine derivate.
The pyridine derivate of 104 structure of formula is preferably made according to the following steps:
4-aminopyridine, triethylamine and methylene chloride are mixed, the reaction of 2- chloracetyl chloride is added dropwise, obtains 104 structure of formula
Pyridine derivate.
The quinoline of 105 structure of formula is preferably made according to the following steps:
8- aminoquinoline, triethylamine and methylene chloride are mixed, the reaction of 2- chloracetyl chloride is added dropwise, obtains 105 structure of formula
Quinoline.
Conductive gold cladding polyimide fiber provided by the invention further includes successively being compounded in the modified polyimide fibre
The palladium metal particle layer and layer gold in dimension table face.In the present invention, the thickness of the layer gold is preferably 0.3~1.0 μm.
The present invention provides a kind of preparation methods of the cladding polyimide fiber of conductive gold described in above-mentioned technical proposal, including
Following steps:
Step A: carrying out basic treatment for polyimide fiber, and cleaning obtains the polyimide fiber of surface carboxylate-containing；
Step B: the obtained fiber of step A being placed in the solution of pyridine derivate or quinoline and is reacted, and cleaning obtains
Polyimide fiber of the surface containing pyridine derivate or quinoline being bonded to ester bond；
Step C: the obtained fiber of step A or step B is placed in palladium salt solution and carries out palladium ion exchange or complexing, clearly
It washes, obtains polyimide fiber of the surface containing palladium ion；
Step D: the polyimide fiber reduction by the surface containing palladium ion, cleaning obtain surface recombination palladium metal grain
The polyimide fiber of sublayer；
Step E: by the polyimide fiber chemical gilding of the surface recombination palladium metal particle layer, cleaning obtains conduction
Gold cladding polyimide fiber.
Polyimide fiber is carried out basic treatment by the present invention, and cleaning obtains the polyimide fiber of surface carboxylate-containing.
In the present invention, the substance that the basic treatment uses preferably uses potassium hydroxide solution；The concentration of the potassium hydroxide solution
For 1~3mol/L.The temperature of the basic treatment is preferably 20~60 DEG C；The time of basic treatment is 10~30min.The present invention
It is preferred that being cleaned using deionized water.The volume ratio for the substance that the quality and basic treatment of the polyimide fiber use for
(200~300) mg:(40~50) mL.
The obtained fiber of step A is placed in the solution of pyridine derivate or quinoline by the present invention to react, and cleaning obtains
Polyimide fiber of the surface containing pyridine derivate or quinoline being bonded to ester bond.In the present invention, the pyridine spreads out
Solvent in the solution of biology or quinoline is preferably selected from water, dimethylformamide, dimethyl acetamide and N- methyl pyrrole
One of pyrrolidone is a variety of.The concentration of the solution of the pyridine derivate or quinoline is preferably 0.5~2mol/L.
The temperature of the reaction is preferably 60~100 DEG C, and the time of reaction is preferably 5~30min.After reaction preferably using go from
Sub- water cleaning, and clean thorough.
The obtained fiber of step A or step B is placed in palladium salt solution and carries out palladium ion exchange or complexing by the present invention, clearly
It washes, obtains polyimide fiber of the surface containing palladium ion.In the present invention, the palladium salt is selected from palladium chloride, palladium acetate, trifluoro second
Sour palladium, trifluoromethanesulfonic acid palladium or palladium sulfate.The concentration of the palladium salt solution is preferably 1~5g/L.The temperature of the exchange or complexing
Degree is 20~60 DEG C, and the time is 5~30min.Fiber after exchange or complexing preferably uses deionized water to clean, and cleans dry
Only.
Polyimide fiber reduction of the present invention by the surface containing palladium ion, cleaning obtain surface recombination palladium metal grain
The polyimide fiber of sublayer.In the present invention, it is described reduction use reducing agent be selected from stannous chloride, dimethylamino borine,
One of sodium hypophosphite, hydrazine hydrate, sodium ascorbate, formaldehyde and formic acid are a variety of.The concentration of the reducing agent is preferably
0.01mol/L~2mol/L.The temperature of the reduction is preferably 10~50 DEG C；The time of reduction is 1~30min.
The polyimide fiber chemical gilding of the surface recombination palladium metal particle layer, cleaning are obtained conduction by the present invention
Gold cladding polyimide fiber.In the present invention, the main salt that chemical gilding uses is selected from sodium chloraurate, potassium chloroaurate and chlorine gold
Acid, in terms of gold ion, the gold salt solution concentration of chemical gilding is 0.2~2.0g/L.The main complexing agent of chemical gilding is thiocarbamide, urine
Element, ammonium hydroxide, pyridine, 4-dimethylaminopyridine, 1- methylimidazole, disodium ethylene diamine tetraacetate, ethylenediamine, sodium sulfite and sulfurous
Any one in sour potassium or two or more combinations, concentration are 0.1mol/L~0.5mol/L；The auxiliary network of chemical gilding
Mixture be citric acid, tartaric acid, lactic acid, malic acid, gluconic acid, acetic acid, propionic acid, glycine, aspartic acid and they
Any one in sodium salt, sylvite and ammonium salt, concentration are 0.1mol/L~1.0mol/L；The reducing agent of chemical gilding is diformazan
Any one or two or more combinations, concentration in amino borane, sodium hypophosphite, hydrazine, sodium ascorbate and formic acid are
0.1mol/L~1.0mol/L；The pH buffer of chemical gilding is selected from NaH2PO4,KH2PO4,Na2HPO4And K2HPO4In it is any
Or it is a variety of, concentration is 0.1mol/L~0.5mol/L.The pH value of plating solution is 3~9 when chemical gilding.The temperature of chemical gilding is excellent
It is selected as 20~70 DEG C.
Method provided by the invention is applied widely, is suitble to the polyimide fiber of a variety of systems, while being suitble to serialization
Production.
The cladding polyimide fiber mechanical property loss late of conductive gold prepared by the present invention is low, electric conductivity and electromagnetic screen
Cover functional, use temperature range is wide, can be used as antistatic, shielding material obtains in some corrosivity and oxidative environment
Using.
In order to further illustrate the present invention, sub- to a kind of conductive gold cladding polyamides provided by the invention below with reference to embodiment
Amine fiber and preparation method thereof is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Preparative Example 1
2-aminopyridine (47.0g, 0.5mol) and triethylamine (104.2mL, 0.75mol) are dissolved in methylene chloride
In (300.0mL), it is anti-to drip room temperature after finishing in 0 DEG C~20 DEG C dropwise addition 2- chloracetyl chlorides (62.1g, 0.55mol) for control reaction temperature
Answer 3h.Water (100.0mL) is added to continue to stir 1h, separates water phase, organic phase is with saturated sodium bicarbonate aqueous solution (100.0mL)
It washes, organic phase is dry with anhydrous sodium sulfate, filters out desiccant, steams methylene chloride, vacuum drying obtains reddish Solid
(76.8g, yield: 90%), i.e. and pyridine derivate shown in 102 structure of formula.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)。
Preparative Example 2
It is reaction raw materials with 3- aminopyridine, for preparation process with Preparative Example 1, product is white solid, i.e. 103 knot of formula
Pyridine derivate shown in structure, yield: 80.2g, yield: 94%.1H NMR(400MHz,D2O): δ 9.16 (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).
Preparative Example 3
4-aminopyridine (47.0g, 0.5mol) and triethylamine (104.2mL, 0.75mol) are dissolved in methylene chloride
In (300.0mL), it is anti-to drip room temperature after finishing in 0 DEG C~20 DEG C dropwise addition 2- chloracetyl chlorides (62.1g, 0.55mol) for control reaction temperature
Answer 6h.Water (100.0mL) is added to continue to stir 1h, separates water phase, organic phase is with saturated sodium bicarbonate aqueous solution (100.0mL)
Wash, organic phase is dry with anhydrous sodium sulfate, filters out desiccant, steam methylene chloride, vacuum drying obtain white solid (77.6g,
Yield: 91%), i.e. and pyridine derivate shown in 104 structure of formula.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).
Preparative Example 4
8- aminoquinoline (72.1g, 0.5mol) and triethylamine (104.2mL, 0.75mol) are dissolved in methylene chloride
In (500.0mL), it is anti-to drip room temperature after finishing in 0 DEG C~20 DEG C dropwise addition 2- chloracetyl chlorides (62.1g, 0.55mol) for control reaction temperature
Answer 3h.Water (150.0mL) is added to continue to stir 1h, separates water phase, organic phase is with saturated sodium bicarbonate aqueous solution (150.0mL)
It washes, organic phase is dry with anhydrous sodium sulfate, filters out desiccant, petroleum ether (200.0mL) is added after steaming methylene chloride, stirring
It filtered after 30min, be dried in vacuo and obtain reddish Solid (107.0g, yield: 97%), i.e. the quinoline of structure shown in formula 105 spreads out
Biology.1H NMR(400MHz,CDCl3): δ 4.43-4.22 (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).
Embodiment 1
Step A: by polyimide fiber in the potassium hydroxide solution of 2mol/L 50 DEG C of processing 10min, use deionized water
Potassium hydroxide is cleaned up, the polyimide fiber of surface potassium containing carboxylic acid is obtained.
Step C: fiber obtained in step A being immersed in the dimethyl formamide solution (3g/L) of 20 DEG C of palladium chloride,
It is cleaned up after 5min with deionized water, obtains the polyimide fiber of surface complexing palladium ion.
Step D: fiber obtained in C is immersed in 20 DEG C of dimethylamino Borane solution (0.1mol/L) and carries out chemistry also
Former 5min, is then cleaned up with deionized water, obtains polyimide fiber of the surface containing ultra-thin palladium metal layer.
Step E: fiber obtained in step D is immersed in 50 DEG C of chemical gilding solution (sodium chloraurate 0.5g/L, acetic acid
20g/L, disodium ethylene diamine tetraacetate 8g/L, formic acid 10mL/L, trisodium citrate 30g/L, K2HPO430g/L, pH 5~6) in
30min is kept, is cleaned up with deionized water, gold cladding polyimide fiber is obtained after drying.
It is the thermal shock resistance test chart of gold cladding polyimide fiber prepared by the embodiment of the present invention 1 referring to Fig. 1, Fig. 1；Its
In, A is the scanning electron microscope (SEM) photograph before the thermal shock resistance test of gold cladding polyimide fiber；B is gold cladding polyimide fiber
Scanning electron microscope (SEM) photograph after thermal shock resistance test.As can be seen from Figure 1: conductive gold cladding polyimide fiber prepared by the present invention is -180
DEG C~200 DEG C of circulations fall off for 10 times without metal, thermal shock resistance with higher.
Embodiment 2
Step A: with embodiment 1.
Step B: fiber obtained in step A is immersed to the DMF solution (0.5mol/L) of 80 DEG C of 101 structures containing formula, 5min
It is cleaned up afterwards with deionized water, obtains the polyimide fiber of 101 structure of surface bond formula.
Step C: with embodiment 1.
Step D: with embodiment 1.
Step E: with embodiment 1.
Embodiment 3
Step A: with embodiment 1.
Step B: fiber obtained in step A is immersed to the DMF solution (0.5mol/L) of 60 DEG C of 102 structures containing formula, 5min
It is cleaned up afterwards with deionized water, obtains the polyimide fiber of 102 structure of surface bond formula.
Step C: with embodiment 1.
Step D: with embodiment 1.
Step E: with embodiment 1.
Embodiment 4
Step A: with embodiment 1.
Step B: fiber obtained in step A is immersed to the DMF solution (0.5mol/L) of 60 DEG C of 103 structures containing formula, 5min
It is cleaned up afterwards with deionized water, obtains the polyimide fiber of 103 structure of surface bond formula.
Step C: with embodiment 1.
Step D: with embodiment 1.
Step E: with embodiment 1.
Fig. 2 is the thermal shock resistance test chart of gold cladding polyimide fiber prepared by the embodiment of the present invention 4, wherein A is gold
Scanning electron microscope (SEM) photograph before coating the thermal shock resistance test of polyimide fiber；B be gold cladding -180 DEG C of polyimide fiber warp~
200 DEG C circulation 10 times after thermal shock resistance test scanning electron microscope (SEM) photograph.As can be seen from Figure 2: conductive gold packet prepared by the present invention
It covers polyimide fiber and is recycled 10 times at -180 DEG C~200 DEG C and fallen off without metal, thermal shock resistance with higher.
Embodiment 5
Step A: with embodiment 1.
Step B: fiber obtained in step A is immersed to the DMF solution (0.5mol/L) of 60 DEG C of 104 structures containing formula, 5min
It is cleaned up afterwards with deionized water, obtains the polyimide fiber of 104 structure of surface bond formula.
Step C: with embodiment 1.
Step D: with embodiment 1.
Step E: with embodiment 1.
Embodiment 6
Step A: with embodiment 1.
Step B: fiber obtained in step A is immersed to the DMF solution (0.5mol/L) of 60 DEG C of 105 structures containing formula, 5min
It is cleaned up afterwards with deionized water, obtains the polyimide fiber of 105 structure of surface bond formula.
Step C: with embodiment 1.
Step D: with embodiment 1.
Step E: with embodiment 1.
Embodiment 7
Step A: with embodiment 1.
Step B: fiber obtained in step A is immersed to the DMF solution (0.5mol/L) of 60 DEG C of 103 structures containing formula, 5min
It is cleaned up afterwards with deionized water, obtains the polyimide fiber of 103 structure of surface bond formula.
Step C: with embodiment 1.
Step D: with embodiment 1.
Step E: fiber obtained in step D is immersed in 20 DEG C of chemical gilding solution (sodium chloraurate 0.5g/L, urea
25g/L, sodium sulfite 8g/L, trisodium citrate 30g/L, sodium ascorbate 5g/L, K2HPO430g/L, pH 8~9) in keep
30min is cleaned up with deionized water, and gold cladding polyimide fiber is obtained after drying.
Embodiment 8
Step A: with embodiment 1.
Step B: with embodiment 7.
Step C: with embodiment 1.
Step D: with embodiment 1.
Step E: fiber obtained in step D is immersed in 20 DEG C of chemical gilding solution (sodium chloraurate 0.5g/L, sulfurous
Sour sodium 8g/L, trisodium citrate 30g/L, sodium hypophosphite 12g/L, K2HPO430g/L, pH 8~9) in keep 30min, spend from
Sub- water cleans up, and gold-plated polyimide fiber is obtained after drying.
The present invention carries out electric conductivity test, knot to gold-plated polyimide fiber prepared by above embodiments 1~2,4 and 6~8
Fruit is shown in Table 1:
The conductivity results of the gold-plated polyimide fiber of the preparation of 1 Examples 1 to 2 of table, 4 and 6~8
The gold-plated polyimide fiber that the present invention prepares above embodiments 1,4,7 and 8 has carried out acid and alkali resistance and antigen
Oxygen performance test, is shown in Table 2~4.The result shows that the gold-plated polyimide fiber modified without pyridine derivate or quinoline
Conductivity in corrosive environment and oxidative environment is able to maintain, but the decaying of its mechanical property is obvious, especially in alkali
In property environment and oxidative environment.Unevenly lead to gold plate short texture this is mainly due to palladium active layer, surface is also not only
Caused by cunning, Fig. 1 is seen.This loose structure will lead to acid, alkali and oxygen atom and enter, to corrode fiber, make its mechanical property
Decline；Through the modified gold-plated polyimide fiber of pyridine derivate or quinoline in corrosive environment and oxidative environment
Conductivity and fibrous mechanical property can keep, fibers gold coating structure is fine and close, surface is smooth, sees Fig. 2.
The acid-resistant corrosion result of the gold-plated polyimide fiber of 2 embodiment 1,4,7 and 8 of table preparation
Note: A is freshly prepd gold-plated polyimide fiber；B is gold-plated after 1mol/L salt acid soak 100h at 80 DEG C
Polyimide fiber
The alkali corrosion resistance result of the gold-plated polyimide fiber of 3 embodiment 1,4,7 and 8 of table preparation
Note: A is freshly prepd gold-plated polyimide fiber；B is to impregnate at 80 DEG C through 2mol/L sodium hydrate aqueous solution
The anti-atomic oxygen corrosion of the gold-plated polyimide fiber of 4 embodiment 1,4,7 and 8 of gold-plated polyimide fiber table preparation after 100h
Property result
Note: A is freshly prepd gold-plated polyimide fiber；B is through 3.2 × 1020atoms/cm2After the processing of dosage elemental oxygen
Gold-plated polyimide fiber
As seen from the above embodiment, the present invention provides a kind of conductive golds to coat polyimide fiber, including modified polyamides
Imine fiber；And successively it is compounded in the palladium metal particle layer and layer gold of the modified polyimide fiber surface；The modification is poly-
Imide fiber is the polyimide fiber of surface carboxylate-containing or contains pyridine derivate or quinoline by the surface that ester bond is bonded
The polyimide fiber of derivative.Fiber provided by the invention is using polyimide fiber as base fibre, by using carboxylate or ester
Key bonding pyridine derivate or quinoline are modified, so that the thermal shock resistance of gold-plated fiber improves.Conductivity is higher, also
It is wide with excellent corrosion resistance and inoxidizability, use temperature range.The results showed that conductive gold cladding polyimides is fine
Dimension is good in -180 DEG C~200 DEG C of thermal shock resistance, recycles 10 times and falls off without metal；Conductivity is 4.53 × 103~1.87
×104S/cm；Conductive gold coats conductivity of the polyimide fiber in acid, alkali and atomic oxygen environment and keeps substantially, but not
It is obvious through the modified fibrous mechanical property decaying of pyridine derivate or quinoline, especially in alkaline environment and elemental oxygen ring
In border.Through the modified gold-plated polyimide fiber of pyridine derivate or quinoline in corrosive environment and oxidative environment
Conductivity and fibrous mechanical property can keep.Intensity at 80 DEG C of gold-plated polyimide fiber before 1mol/L salt acid soak
For 12.14~12.51cN/dtex, still reach 11.49~12.55cN/dtex after impregnating 100h；Modulus before acid soak is
Modulus is 584.01~601.38cN/dtex after 597.43~606.47cN/dtex, acid soak 100h；Fracture is stretched before acid soak
Long rate is 3.74~3.84%, is 3.86~4.16% after acid soak；Conductivity is 4.53 × 10 before acid soak3~1.87 ×
104Conductivity after S/cm, acid soak 100h is 4.60 × 103~1.90 × 104S/cm.At 80 DEG C of gold-plated polyimide fiber
Intensity after 2mol/L sodium hydrate aqueous solution impregnates 100h is 5.52~12.60cN/dtex；Modulus be 242.61~
606.13cN/dtex；Elongation at break is 3.77~5.21%；Conductivity is 4.50 × 103~1.81 × 104S/cm.3.2
×1020atoms/cm2The intensity of dosage elemental oxygen treated gold-plated polyimide fiber is 6.35~12.41cN/dtex；Mould
Amount is 418.74~602.87cN/dtex；Elongation at break is 3.70~4.74%；Conductivity is 4.55 × 103~1.84 ×
104S/cm。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of conductive gold coats polyimide fiber, which is characterized in that including modified polyimide fiber；
And successively it is compounded in the palladium metal particle layer and layer gold of the modified polyimide fiber surface；
The modified polyimide fiber is the polyimide fiber of surface carboxylate-containing or contains pyrrole by the surface that ester bond is bonded
The polyimide fiber of piperidine derivatives or quinoline.
2. conductive gold according to claim 1 coats polyimide fiber, which is characterized in that described to be bonded by ester bond
Surface is made containing the polyimide fiber of pyridine derivate or quinoline by following methods:
The polyimide fiber of surface carboxylate-containing is placed in the solution of pyridine derivate or quinoline and is reacted, cleaning system
?.
3. conductive gold according to claim 1 coats polyimide fiber, which is characterized in that the pyridine derivate is selected from
Formula 101, formula 102, formula 103 or formula 104；The quinoline is selected from formula 105；
4. a kind of preparation method of any one of claims 1 to 3 conductive gold cladding polyimide fiber, including following step
It is rapid:
Step A: carrying out basic treatment for polyimide fiber, and cleaning obtains the polyimide fiber of surface carboxylate-containing；
Step B: the obtained fiber of step A being placed in the solution of pyridine derivate or quinoline and is reacted, and cleaning obtains ester
Polyimide fiber of the surface containing pyridine derivate or quinoline of key bonding；
Step C: the obtained fiber of step A or step B being placed in palladium salt solution and carries out palladium ion exchange or complexing, and cleaning obtains
Polyimide fiber to surface containing palladium ion；
Step D: the polyimide fiber reduction by the surface containing palladium ion, cleaning obtain surface recombination palladium metal particle layer
Polyimide fiber；
Step E: by the polyimide fiber chemical gilding of the surface recombination palladium metal particle layer, cleaning obtains conductive gold packet
Cover polyimide fiber.
5. the preparation method according to claim 4, which is characterized in that the alkali process uses potassium hydroxide；At the alkali
The temperature of reason is 20~60 DEG C；The time of the alkali process is 10~30min.
6. the preparation method according to claim 4, which is characterized in that the solution of the pyridine derivate or quinoline
In solvent be selected from one of water, dimethylformamide, dimethyl acetamide and N-Methyl pyrrolidone or a variety of；
The concentration of the solution of the pyridine derivate or quinoline is 0.5~2mol/L.
7. the preparation method according to claim 4, which is characterized in that the temperature reacted in the step B is 60~100
℃；The time of reaction is 5~30min.
8. the preparation method according to claim 4, which is characterized in that palladium salt is selected from palladium chloride, acetic acid in the step C
Palladium, palladium trifluoroacetate, trifluoromethanesulfonic acid palladium or palladium sulfate.
9. the preparation method according to claim 4, which is characterized in that the temperature for exchanging or being complexed in the step C is 20
~60 DEG C, the time is 5~30min.
10. the preparation method according to claim 4, which is characterized in that the reducing agent for restoring use in the step D is selected from
One of stannous chloride, dimethylamino borine, sodium hypophosphite, hydrazine hydrate, sodium ascorbate, formaldehyde and formic acid are a variety of；
The temperature of the reduction is 10~50 DEG C；The time of reduction is 1~30min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114657765A (en) * | 2022-04-26 | 2022-06-24 | 朱健 | Corrosion-resistant waterproof fabric and preparation method thereof |
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