CN114790591A - Polyimide/polyaniline composite conductive fiber membrane material and preparation method thereof - Google Patents
Polyimide/polyaniline composite conductive fiber membrane material and preparation method thereof Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 156
- 239000004642 Polyimide Substances 0.000 title claims abstract description 87
- 229920001721 polyimide Polymers 0.000 title claims abstract description 87
- 239000000835 fiber Substances 0.000 title claims abstract description 69
- 239000012528 membrane Substances 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000009987 spinning Methods 0.000 claims abstract description 83
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002253 acid Substances 0.000 claims abstract description 42
- 239000010410 layer Substances 0.000 claims abstract description 26
- 239000012792 core layer Substances 0.000 claims abstract description 22
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- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000010556 emulsion polymerization method Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 120
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 57
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 48
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 37
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 36
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000004697 Polyetherimide Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 229920001601 polyetherimide Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 230000009471 action Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
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- 238000011065 in-situ storage Methods 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The invention discloses a polyimide/polyaniline composite conductive fiber membrane material, which is in a coaxial fiber structure; the core layer is a polyimide layer, and the shell layer is a polyaniline layer. The invention also provides a preparation method of the composite conductive fibrous membrane material, which comprises the following steps: (1) preparing protonic acid doped polyaniline by using aniline as a raw material through an emulsion polymerization method, preparing dedoped polyaniline through dedoping, and preparing a polyaniline spinning solution through secondary doping; (2) dissolving soluble polyimide serving as a raw material in an organic solvent to prepare a polyimide spinning solution; (3) the polyaniline spinning solution is used as a shell layer spinning solution, the polyimide spinning solution is used as a core layer spinning solution, and the polyimide/polyaniline composite conductive fiber membrane material is prepared by adopting coaxial electrostatic spinning. The polyimide/polyaniline composite conductive fiber membrane material prepared by the invention has a unique pore structure, good flexibility and conductivity, simple preparation steps, short period and low cost.
Description
Technical Field
The invention relates to the technical field of conductive composite materials, in particular to a polyimide/polyaniline composite conductive fiber membrane material and a preparation method thereof.
Background
In recent years, with the lightness and thinness of electronic devices and the intellectualization of wearable devices, flexible electronic technology has become the leading edge of technology and the hot research field of the present day, and various portable and wearable electronic devices are produced accordingly. The appearance of these new electronic devices has also made more demands on the flexibility of various devices while enriching people's lives. The performance of the flexible conductive material serving as an important component of the flexible electronic device is a bottleneck problem which restricts the further development of the flexible electrode technology in various directions, so that the research and development of the high-performance flexible conductive material have important significance for the development of the field of flexible electronics.
Polyaniline is a common conductive polymer, and has great application advantages in many fields due to low cost, easily available raw materials, simple synthesis process, excellent physicochemical characteristics, diversified structural design, unique doping mode and good environmental stability, so that the polyaniline is widely researched. As a mature method for simply and efficiently preparing the superfine fiber membrane at present, high-voltage electrostatic spinning can achieve the purpose of controlling the form and the porosity of the nanofiber by changing a high-molecular precursor, adding various filling particles and changing process parameters, thereby obtaining wide attention of various national scholars. The polyimide fiber prepared by the technology can obtain a fiber membrane material which has small fiber diameter, uniform distribution, high specific surface area, high porosity, narrow pore size distribution and excellent corrosion resistance. However, because polyaniline molecular chains have strong rigidity and poor dissolution and processing performances, the research of combining and applying an electrostatic spinning technology with conductive polyaniline mainly focuses on two aspects, on one hand, polyaniline is directly used for electrostatic spinning, but because polyaniline is difficult to process, a spinning aid (such as polyethylene oxide) is usually used for dissolving or dispersing a small amount of polyaniline to prepare a spinning solution with high viscosity and stable properties for spinning at present, however, because the spinning aid is usually an insulating high polymer material, and the amount of the polyaniline which can be dissolved or dispersed in the solution is small, and generally only accounts for 0.5-3 wt% of the total mass of the solution, the conductivity of the prepared fiber membrane is poor; or strong acid (such as concentrated sulfuric acid) is adopted as a solvent to be dissolved for spinning so as to obtain spinning solution with higher concentration, but the strong acid such as the concentrated sulfuric acid has stronger corrosivity, puts more rigorous requirements on spinning equipment and personnel operation, and the strength of the prepared fiber is poorer; on the other hand, the surface of the prepared electro-spinning fibrous membrane base material is coated with the acid-doped polyaniline with the conductive characteristic by utilizing an in-situ growth technology, and most of the base material is a carbon fiber membrane material prepared by electro-spinning and high-temperature carbonization of a high polymer solution, so that the preparation process is complex, the large-scale production of the material is not facilitated, and the process requirement is very strict. In the in-situ polymerization process, the polymerization of polyaniline on the fiber surface is generally random, and is difficult to uniformly coat all the fiber surfaces, so that the unique pore structure of the fiber membrane is easily damaged, and the application performance of the fiber membrane is influenced. Therefore, how to prepare a high-concentration and stable polyaniline solution so as to directly introduce polyaniline into fibers or on the surfaces of the fibers during high-voltage electrostatic spinning has important significance in obtaining a flexible polyaniline-based fiber membrane with a better pore structure and an excellent conductive function by adjusting process parameters.
Disclosure of Invention
The present invention is directed to solving the above-mentioned problems of the prior art. The invention provides a polyimide/polyaniline composite conductive fiber membrane material and a preparation method thereof, and the prepared polyimide/polyaniline composite conductive fiber membrane material has a unique pore structure, good flexibility and conductivity, simple preparation steps, short period and low cost.
In order to solve the technical problems, the embodiment of the invention discloses a polyimide/polyaniline composite conductive fiber membrane material which is a coaxial fiber structure;
the core layer of the coaxial fiber structure is a polyimide layer, and the shell layer is a polyaniline layer.
The embodiment of the invention also discloses a preparation method of the polyimide/polyaniline composite conductive fiber membrane material, which comprises the following steps:
(1) preparing protonic acid doped polyaniline from aniline serving as a raw material by an emulsion polymerization method, preparing dedoped polyaniline by dedoping the protonic acid doped polyaniline, and preparing a polyaniline spinning solution by secondarily doping the dedoped polyaniline;
(2) dissolving soluble polyimide serving as a raw material in an organic solvent to prepare a polyimide spinning solution;
(3) and (2) preparing coaxial composite fibers by using the polyaniline spinning solution as a shell layer spinning solution and the polyimide spinning solution as a core layer spinning solution and adopting coaxial electrostatic spinning to obtain the polyimide/polyaniline composite conductive fiber membrane material.
Further, the organic solvent is any one or the combination of two of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Further, the protective gas is one of nitrogen or argon.
Further, the mass fraction of polyaniline in the polyaniline spinning solution is 7.5-16 wt%, and the mass fraction of polyimide in the polyimide spinning solution is 15-25 wt%.
Further, in the step (1), the protonic acid doped polyaniline is prepared by the following steps:
respectively dissolving protonic acid and Ammonium Persulfate (APS) in deionized water at normal temperature and normal pressure to prepare a protonic acid aqueous solution and AN ammonium persulfate aqueous solution, adding Aniline (AN) into the protonic acid aqueous solution under the atmosphere of protective gas, carrying out magnetic stirring reaction for 30-60 min, then dropwise adding the ammonium persulfate aqueous solution into a mixed solution of aniline and protonic acid, controlling the reaction temperature to be 0-5 ℃, carrying out continuous magnetic stirring reaction for 2-10 h, then filtering, washing to be neutral, and carrying out vacuum drying at 50-70 ℃ for 12-48 h to obtain the protonic acid doped polyaniline;
wherein the mass ratio of the aniline to the protonic acid is 1: 0.5-2.5, and the mass ratio of the aniline to the ammonium persulfate is 1: 0.5-2.5.
Further, in the step (1), the dedoping comprises the following steps:
dispersing the protonic acid doped polyaniline in ammonia water with the concentration of 1mol/L according to the ratio of the mass of the protonic acid doped polyaniline to the volume of the ammonia water of 1g: 100-500 mL, carrying out magnetic stirring reaction for 10-24 h, filtering, washing to be neutral, and carrying out vacuum drying at 50-70 ℃ for 12-48 h to obtain the dedoped polyaniline.
Further, in the step (1), the secondary doping comprises the following steps: mixing the dedoped polyaniline, morpholine and an organic solvent according to the mass ratio of 1: 6-15, stirring for 10-20 min at 80 ℃ by magnetic force to completely dissolve the dedoped polyaniline, morpholine and the organic solvent, heating the solution to 130 ℃, evaporating the morpholine and the redundant organic solvent, cooling to room temperature after the total mass of the polyaniline solution is reduced by 50% -75%, adding protonic acid into the polyaniline solution, and changing the blue color of the solution into dark green after the polyaniline solution is completely dissolved to obtain the polyaniline spinning solution;
in the secondary doping, the mass ratio of the dedoped polyaniline to the protonic acid is 1: 0.2-2.
Further, in the step (2), the polyimide spinning solution is prepared by the following steps:
adding a certain amount of soluble polyimide into a mixed solvent of N, N-dimethylformamide and N-methylpyrrolidone at normal temperature and normal pressure, and stirring and reacting at 60-80 ℃ for 2-10 hours to prepare the polyimide spinning solution;
wherein the mass ratio of the N, N-dimethylformamide to the N-methylpyrrolidone is 1: 1-7.
Further, in the step (3), in the electrostatic spinning process, a coaxial stainless steel needle is adopted, the flow rate ratio of the core layer spinning solution to the shell layer spinning solution is 1: 0.1-5, high-voltage electrostatic spinning is carried out under the action of a high-voltage electric field with the voltage of 10-30 kV, the spinning time is 2-10 hours, a roller with a certain rotating speed is used as a receiving end for collection, then the collection is carried out by soaking in water, demoulding is carried out, and vacuum drying is carried out for 12-48 hours at the temperature of 50-70 ℃, so that the polyimide/polyaniline composite conductive fiber membrane material is prepared. Wherein, the coaxial stainless steel needle inner/outer needle is any one of 15G/20G, 17G/22G and 18G/25G.
Further, the soluble polyimide is one of polyetherimide or fluorine-containing polyimide.
Further, the protonic acid is any one of camphorsulfonic acid (CSA), dodecylbenzene sulfonic acid (DBSA) and 2-acrylamido-2-methyl-1-propane sulfonic Acid (AMPS).
Compared with the prior art, the invention has the following technical effects:
the preparation method comprises the steps of preparing protonic acid doped polyaniline by an emulsion polymerization method, carrying out de-doping under the action of ammonia water, dissolving the solution in a corresponding solvent, and carrying out secondary doping by adopting protonic acid to prepare a polyaniline spinning solution; then, the soluble polyimide spinning solution is used as a core layer, the polyaniline spinning solution is used as a shell layer, and the coaxial electrospinning polyimide/polyaniline composite conductive fiber membrane material is prepared by a coaxial high-voltage electrostatic spinning technology. The composite conductive fiber membrane material with the core-shell structure is prepared by taking polyimide with excellent mechanical property as a core layer supporting material and taking protonic acid-doped conductive polyaniline as a shell layer conductive material, and the fiber membrane material has the characteristics of light weight, good flexibility, unique fiber and pore structure, controllable preparation size and thickness and the like on the basis of better conductive property, has good application prospect in the field of flexible electronic devices, and particularly has obvious advantages in the field of multifunctional integration requirements such as flexible energy storage, sensing and the like.
Drawings
FIG. 1 shows SEM images of polyimide/polyaniline composite conductive fiber membrane material of example 1 of the present invention at different magnifications ((a)2000 times, (b)5000 times and (c)10000 times);
FIG. 2 is an SEM image showing the different magnifications ((a)2000 times, (b)5000 times and (c)10000 times) of the polyimide/polyaniline composite conductive fiber membrane material of example 2 of the present invention;
FIG. 3 is SEM images of the polyimide/polyaniline composite conductive fiber membrane material of example 3 of the present invention at different magnifications ((a)2000 × (b)5000 × (c)10000 ×);
fig. 4 is a diagram showing the shape change of the polyimide/polyaniline composite conductive fiber membrane material of examples 1 to 4 of the present invention in the natural state, the twisted state, and the bent state in this order: (a) example 1; (b) example 2; (c) example 3; (d) example 4.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure. While the invention will be described in conjunction with the preferred embodiments, it is not intended that features of the invention be limited to these embodiments. On the contrary, the invention has been described in connection with the embodiments for the purpose of covering alternatives or modifications as may be extended based on the claims of the invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be practiced without these particulars. Moreover, some of the specific details have been left out of the description in order to avoid obscuring or obscuring the focus of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
(1) Preparing polyaniline spinning solution: respectively dissolving 20g of 2-acrylamido-2-methyl-1-propanesulfonic Acid (AMPS) and 10g of Ammonium Persulfate (APS) in 80mL of deionized water and 40mL of deionized water at normal temperature and normal pressure, adding aniline into a 2-acrylamido-2-methyl-1-propanesulfonic Acid (AMPS) aqueous solution in a protective gas atmosphere according to the mass ratio of 1:2.5 of aniline to protonic acid, stirring magnetically for 30-60 min, dropwise adding an ammonium persulfate aqueous solution into a mixed solution of aniline and protonic acid according to the mass ratio of 1:1.5 of aniline to protonic acid, reacting at the temperature of 0-5 ℃, continuously stirring magnetically for 8h, filtering, washing to neutrality, and drying in vacuum at the temperature of 60 ℃ for 24h to obtain AMPS doped polyaniline;
according to the volume ratio of the mass of the AMPS doped polyaniline to the volume of ammonia water of 1g:300mL, dispersing 5g of AMPS doped polyaniline in 1M ammonia water, magnetically stirring for reaction for 12h, filtering again, washing to neutrality, and vacuum-drying at 50 ℃ for 24 h;
according to the mass ratio of 1:7:7 of dedoping polyaniline to morpholine to organic solvent, 0.6g of dried dedoping polyaniline is dissolved in morpholine and N, N-dimethylformamide, the solution is heated to 130 ℃ after the dedoping polyaniline and the organic solvent are completely dissolved by magnetic stirring at 80 ℃ for 10min, morpholine and redundant N, N-dimethylformamide are evaporated out, after the total mass of the solution is reduced to 44.4%, the solution is cooled to room temperature, 0.6g of AMPS is added into the polyaniline solution according to the mass ratio of 1:1 of dedoping polyaniline to AMPS, after the solution is completely dissolved, the solution is changed from blue to dark green, and the polyaniline spinning solution with the mass fraction of 15 wt% of polyaniline is prepared;
(2) preparing a polyimide spinning solution: adding 6.0g of polyetherimide into a mixed solvent of 6.68mL of N, N-dimethylformamide and 12.32mL of N-methylpyrrolidone at normal temperature and normal pressure, and stirring for 5 hours at 60-80 ℃ to prepare a polyimide spinning solution with the polyimide mass fraction of 24 wt%;
(3) preparing a polyimide/polyaniline composite conductive fiber membrane material: the preparation method comprises the steps of taking a polyimide spinning solution as a core layer spinning solution, taking a polyaniline spinning solution as a shell layer spinning solution, carrying out high-voltage electrostatic spinning under the action of a high-voltage electric field with the voltage of 10kV by adopting a coaxial stainless steel needle with an inner needle head/outer needle head type of 17G/22G, taking the flow rate of a core layer solution as 0.1mL/h and the flow rate of a shell layer solution as 0.1mL/h, collecting the core layer solution and the shell layer solution with a roller with a certain rotating speed as a receiving end, carrying out spinning for 6h, soaking the core layer solution in water to demould the core layer solution, and preparing a polyimide/polyaniline composite conductive fiber membrane material, wherein the conductivity of the obtained composite conductive fiber membrane is 0.33S/cm.
Example 2
(1) Preparing polyaniline spinning solution: respectively dissolving 20g of 2-acrylamido-2-methyl-1-propanesulfonic Acid (AMPS) and 10g of Ammonium Persulfate (APS) in 80mL of deionized water and 40mL of deionized water at normal temperature and normal pressure, adding aniline into an aqueous solution of 2-acrylamido-2-methyl-1-propanesulfonic Acid (AMPS) in a protective gas atmosphere according to the mass ratio of the aniline to the protonic acid of 1:2.5, stirring magnetically for 30-60 min, dropwise adding an aqueous solution of ammonium persulfate into a mixed solution of the aniline and the protonic acid according to the mass ratio of the aniline to the ammonium persulfate of 1:1.5, reacting at the temperature of 0-5 ℃, continuously stirring magnetically for 8 hours, filtering and washing to neutrality, and drying in vacuum at the temperature of 60 ℃ for 24 hours to obtain the AMPS-doped polyaniline;
according to the method, 5g of AMPS doped polyaniline is dispersed in ammonia water with the concentration of 1M according to the ratio of the mass of AMPS doped polyaniline to the volume of the ammonia water of 1g:300mL, the mixture is magnetically stirred to react for 12 hours, and then the mixture is filtered, washed to be neutral and dried in vacuum for 24 hours at the temperature of 50 ℃;
dissolving 0.6g of dried dedoping polyaniline in morpholine and N, N-dimethylformamide according to the mass ratio of 1:7:7, magnetically stirring the solution at 80 ℃ for 10min to completely dissolve the dried dedoping polyaniline, the morpholine and the N, N-dimethylformamide, heating the solution to 130 ℃, evaporating the morpholine and the redundant N, N-dimethylformamide to remove the morpholine and the redundant N, N-dimethylformamide until the total mass of the solution is reduced to 44.4%, cooling the solution to room temperature, adding 0.6g of AMPS into the polyaniline solution according to the mass ratio of the dedoping polyaniline to the AMPS of 1:1, and changing the blue color of the solution into dark green color after the solution is completely dissolved to prepare a polyaniline spinning solution with the mass fraction of 15 wt%;
(2) preparing a polyimide spinning solution: adding 6.0g of polyetherimide into a mixed solvent of 6.68mL of N, N-dimethylformamide and 12.32mL of N-methylpyrrolidone at normal temperature and normal pressure, and stirring for 5 hours at 60-80 ℃ to obtain a polyimide spinning solution with the polyimide mass fraction of 24 wt%;
(3) preparing a polyimide/polyaniline composite conductive fiber membrane material: the polyimide spinning solution is used as a core layer spinning solution, the polyaniline spinning solution is used as a shell layer spinning solution, a coaxial stainless steel needle with an inner needle head/outer needle head type of 17G/22G is adopted, the flow rate of a core layer solution is 0.1mL/h, the flow rate of a shell layer solution is 0.3mL/h, high-voltage electrostatic spinning is carried out under the action of a high-voltage electric field with the voltage of 10kV, a roller with a certain rotating speed is used as a receiving end for collection, the spinning time is 6h, then the polyimide/polyaniline composite conductive fiber membrane material is obtained by soaking in water to demould the polyimide/polyaniline composite conductive fiber membrane material, and the conductivity of the obtained composite conductive fiber membrane is 0.25S/cm.
Example 3
(1) Preparing a polyaniline spinning solution: respectively dissolving 20g of 2-acrylamido-2-methyl-1-propanesulfonic Acid (AMPS) and 10g of Ammonium Persulfate (APS) in 80mL of deionized water and 40mL of deionized water at normal temperature and normal pressure, adding aniline into an aqueous solution of 2-acrylamido-2-methyl-1-propanesulfonic Acid (AMPS) in a protective gas atmosphere according to the mass ratio of the aniline to the protonic acid of 1:2.5, stirring magnetically for 30-60 min, dropwise adding an aqueous solution of ammonium persulfate into a mixed solution of the aniline and the protonic acid according to the mass ratio of the aniline to the ammonium persulfate of 1:1.5, reacting at the temperature of 0-5 ℃, continuously stirring magnetically for 8 hours, filtering and washing to neutrality, and drying in vacuum at the temperature of 60 ℃ for 24 hours to obtain the AMPS-doped polyaniline;
according to the volume ratio of the mass of the AMPS doped polyaniline to the volume of ammonia water of 1g:300mL, dispersing 5g of AMPS doped polyaniline in 1M ammonia water, magnetically stirring for reaction for 12h, filtering again, washing to neutrality, and vacuum-drying at 50 ℃ for 24 h;
according to the mass ratio of 1:7:7 of dedoping polyaniline to morpholine to organic solvent, 0.6g of dried dedoping polyaniline is dissolved in morpholine and N, N-dimethylformamide, the solution is heated to 130 ℃ after the dedoping polyaniline and the organic solvent are completely dissolved by magnetic stirring at 80 ℃ for 10min, morpholine and redundant N, N-dimethylformamide are evaporated out, after the total mass of the solution is reduced to 44.4%, the solution is cooled to room temperature, 0.6g of AMPS is added into the polyaniline solution according to the mass ratio of 1:1 of dedoping polyaniline to AMPS, after the solution is completely dissolved, the solution is changed from blue to dark green, and the polyaniline spinning solution with the mass fraction of 15 wt% of polyaniline is prepared;
(2) preparing a polyimide spinning solution: adding 6.0g of polyetherimide into a mixed solvent of 6.68mL of N, N-dimethylformamide and 12.32mL of N-methylpyrrolidone at normal temperature and normal pressure, and stirring for 5 hours at 60-80 ℃ to prepare a polyimide spinning solution with the polyimide mass fraction of 24 wt%;
(3) preparing a polyimide/polyaniline composite conductive fiber membrane material: the polyimide spinning solution is used as a core layer spinning solution, the polyaniline spinning solution is used as a shell layer spinning solution, a coaxial stainless steel needle with an inner needle head/outer needle head type of 17G/22G is adopted, the flow rate of a core layer solution is 0.3mL/h, the flow rate of a shell layer solution is 0.1mL/h, high-voltage electrostatic spinning is carried out under the action of a high-voltage electric field with the voltage of 10kV, a roller with a certain rotating speed is used as a receiving end for collection, the spinning time is 6h, then the polyimide/polyaniline composite conductive fiber membrane material is obtained by soaking in water to demould, and the membrane conductivity of the obtained composite conductive fiber membrane is 0.76S/cm.
Example 4
(1) Preparing a polyaniline spinning solution: respectively dissolving 20g of 2-acrylamido-2-methyl-1-propanesulfonic Acid (AMPS) and 10g of Ammonium Persulfate (APS) in 80mL of deionized water and 40mL of deionized water at normal temperature and normal pressure, adding aniline into an aqueous solution of 2-acrylamido-2-methyl-1-propanesulfonic Acid (AMPS) in a protective gas atmosphere according to the mass ratio of the aniline to the protonic acid of 1:2.5, stirring magnetically for 30-60 min, dropwise adding an aqueous solution of ammonium persulfate into a mixed solution of the aniline and the protonic acid according to the mass ratio of the aniline to the ammonium persulfate of 1:1.5, reacting at the temperature of 0-5 ℃, continuously stirring magnetically for 8 hours, filtering and washing to neutrality, and drying in vacuum at the temperature of 60 ℃ for 24 hours to obtain the AMPS-doped polyaniline;
according to the volume ratio of the mass of the AMPS doped polyaniline to the volume of ammonia water of 1g:300mL, dispersing 5g of AMPS doped polyaniline in 1M ammonia water, magnetically stirring for reaction for 12h, filtering again, washing to neutrality, and vacuum-drying at 50 ℃ for 24 h;
according to the mass ratio of 1:7:7 of dedoping polyaniline to morpholine to organic solvent, 0.6g of dried dedoping polyaniline is dissolved in morpholine and N, N-dimethylformamide, the solution is heated to 130 ℃ after the dedoping polyaniline and the organic solvent are completely dissolved by magnetic stirring at 80 ℃ for 10min, morpholine and redundant N, N-dimethylformamide are evaporated out, after the total mass of the solution is reduced to 44.4%, the solution is cooled to room temperature, 0.3g of AMPS is added into the polyaniline solution according to the mass ratio of 1:0.5 of dedoping polyaniline to AMPS, after the solution is completely dissolved, the solution is changed from blue to dark green, and polyaniline spinning solution with the mass fraction of 15 wt% of polyaniline is prepared;
(2) preparing a polyimide spinning solution: adding 6.0g of polyetherimide into a mixed solvent of 6.68mL of N, N-dimethylformamide and 12.32mL of N-methylpyrrolidone at normal temperature and normal pressure, and stirring for 5 hours at 60-80 ℃ to prepare a polyimide spinning solution with the polyimide mass fraction of 24 wt%;
(3) preparing a polyimide/polyaniline composite conductive fiber membrane material: the polyimide spinning solution is used as a core layer spinning solution, the polyaniline spinning solution is used as a shell layer spinning solution, a coaxial stainless steel needle with an inner needle head/outer needle head type of 17G/22G is adopted, the flow rate of a core layer solution is 0.3mL/h, the flow rate of a shell layer solution is 0.1mL/h, high-voltage electrostatic spinning is carried out under the action of a high-voltage electric field with the voltage of 10kV, a roller with a certain rotating speed is used as a receiving end for collection, the spinning time is 6h, then the polyimide/polyaniline composite conductive fiber membrane material is obtained by soaking in water to demould, and the membrane conductivity of the obtained composite conductive fiber membrane is 0.18S/cm.
The invention provides a preparation method of a coaxial electrospun polyimide/polyaniline composite conductive fiber membrane material. Firstly, preparing polyaniline doped with protonic acid by an emulsion polymerization method, carrying out de-doping under the action of ammonia water, dissolving the solution in a corresponding solvent, and carrying out secondary doping by adopting protonic acid to prepare a polyaniline spinning solution; then, the soluble polyimide spinning solution is used as a core layer, the polyaniline spinning solution is used as a shell layer, and the coaxial electrospinning polyimide/polyaniline composite conductive fiber membrane material is prepared by a coaxial high-voltage electrostatic spinning technology, so that the problem of polyaniline agglomeration in an in-situ polymerization preparation process is solved. The prepared polyimide/polyaniline composite conductive fiber membrane material has stable chemical property, higher specific surface area, unique pore structure and better flexibility. The preparation method of the coaxial electrospinning polyimide/polyaniline composite conductive fiber membrane material has the advantages of simple preparation steps, short period, low cost and the like, and provides a new idea for preparing the multifunctional three-dimensional porous flexible conductive polymer membrane material with good flexibility, excellent mechanical properties, good conductivity and the like.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a more particular description of the invention than is possible with reference to the specific embodiments, and the specific embodiments of the invention are not to be considered as limited to those descriptions. Various changes in form and detail, including simple deductions or substitutions, may be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (10)
1. A polyimide/polyaniline composite conductive fiber membrane material is characterized in that the composite conductive fiber membrane material is of a coaxial fiber structure;
the core layer of the coaxial fiber structure is a polyimide layer, and the shell layer is a polyaniline layer.
2. The preparation method of the polyimide/polyaniline composite conductive fiber membrane material as claimed in claim 1, comprising the following steps:
(1) preparing protonic acid doped polyaniline from aniline serving as a raw material by an emulsion polymerization method, preparing dedoped polyaniline by dedoping the protonic acid doped polyaniline, and preparing a polyaniline spinning solution by secondarily doping the dedoped polyaniline;
(2) dissolving soluble polyimide serving as a raw material in an organic solvent to prepare a polyimide spinning solution;
(3) and (2) preparing a coaxial composite fiber by using the polyaniline spinning solution as a shell layer spinning solution and the polyimide spinning solution as a core layer spinning solution and adopting coaxial electrostatic spinning to obtain the polyimide/polyaniline composite conductive fiber membrane material.
3. The preparation method of the polyimide/polyaniline composite conductive fiber membrane material as claimed in claim 2, wherein the mass fraction of polyaniline in the polyaniline spinning solution is 7.5-16 wt%, and the mass fraction of polyimide in the polyimide spinning solution is 15-25 wt%.
4. The method for preparing the polyimide/polyaniline composite conductive fiber membrane material as claimed in claim 2, wherein in the step (1), the protonic acid-doped polyaniline is prepared by the following steps:
respectively dissolving protonic acid and ammonium persulfate to prepare protonic acid aqueous solution and ammonium persulfate aqueous solution, adding aniline into the protonic acid aqueous solution under the atmosphere of protective gas, reacting for 30-60 min, dropwise adding the ammonium persulfate aqueous solution into the mixed solution of aniline and protonic acid, controlling the reaction temperature to be 0-5 ℃, reacting for 2-10 h, filtering, washing to be neutral, and vacuum drying to obtain protonic acid doped polyaniline;
wherein the mass ratio of the aniline to the protonic acid is 1: 0.5-2.5, and the mass ratio of the aniline to the ammonium persulfate is 1: 0.5-2.5.
5. The method for preparing the polyimide/polyaniline composite conductive fiber membrane material as claimed in claim 2, wherein in the step (1), the de-doping comprises the steps of:
and dispersing the protonic acid doped polyaniline in ammonia water, reacting for 10-15 h, filtering, washing to neutrality, and drying in vacuum to obtain the dedoped polyaniline.
6. The method for preparing the polyimide/polyaniline composite conductive fiber membrane material as claimed in claim 2, wherein in the step (1), the secondary doping comprises the following steps: mixing the dedoped polyaniline, morpholine and an organic solvent according to the mass ratio of 1: 6-15, stirring until the dedoped polyaniline, morpholine and organic solvent are completely dissolved to form a polyaniline solution, heating the polyaniline solution to 130 ℃, cooling to room temperature after the total mass of the polyaniline solution is reduced by 50% -75%, adding protonic acid into the polyaniline solution, and after the polyaniline solution is completely dissolved, changing the blue color of the solution into dark green to prepare the polyaniline spinning solution;
in the secondary doping, the mass ratio of the dedoping polyaniline to the protonic acid is 1: 0.2-2.
7. The preparation method of the polyimide/polyaniline composite conductive fiber membrane material as claimed in claim 2, wherein in the step (2), the polyimide spinning solution is prepared by the following steps:
adding soluble polyimide into a mixed solvent of N, N-dimethylformamide and N-methylpyrrolidone, and stirring for reacting for 2-10 hours to prepare the polyimide spinning solution;
wherein the mass ratio of the N, N-dimethylformamide to the N-methylpyrrolidone is 1: 1-7.
8. The preparation method of the polyimide/polyaniline composite conductive fiber membrane material as claimed in claim 2, wherein in the step (3), in the electrostatic spinning process, the flow rate ratio of the core layer spinning solution to the shell layer spinning solution is 1: 0.1-5, the control voltage is 10-30 kV, and the spinning time is 2-10 h.
9. The method for preparing the polyimide/polyaniline composite conductive fiber membrane material according to any one of claims 2 to 8, wherein the soluble polyimide is one of polyetherimide or fluorine-containing polyimide.
10. The method for preparing a polyimide/polyaniline composite conductive fiber membrane material according to any one of claims 2 to 8, wherein the protonic acid is any one of camphorsulfonic acid (CSA), dodecylbenzenesulfonic acid (DBSA), 2-acrylamido-2-methyl-1-propanesulfonic Acid (AMPS).
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