CN106637472B - The method that Electrospinning Method prepares polyimides micrometer fibers - Google Patents
The method that Electrospinning Method prepares polyimides micrometer fibers Download PDFInfo
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- CN106637472B CN106637472B CN201611090118.3A CN201611090118A CN106637472B CN 106637472 B CN106637472 B CN 106637472B CN 201611090118 A CN201611090118 A CN 201611090118A CN 106637472 B CN106637472 B CN 106637472B
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- ammonium salt
- acid ammonium
- polyimides
- spinning
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- 239000000835 fiber Substances 0.000 title claims abstract description 81
- 239000004642 Polyimide Substances 0.000 title claims abstract description 48
- 229920001721 polyimide Polymers 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000001523 electrospinning Methods 0.000 title claims abstract description 13
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 131
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 114
- 238000009987 spinning Methods 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 36
- 239000012266 salt solution Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 239000004952 Polyamide Substances 0.000 claims description 10
- 229920002647 polyamide Polymers 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims 1
- -1 amino acid ammonium salt Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 4
- 238000004901 spalling Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
-
- 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
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- 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
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The present invention relates to a kind of preparations of macromolecule electrostatic spinning fiber, more particularly it relates to which the method that Electrospinning Method prepares polyimides micrometer fibers, belongs to technical field of polymer materials.The method that Electrospinning Method prepares polyimides micrometer fibers, comprising the following steps: by the dissolution of polyamic acid ammonium salt with water, obtain polyamic acid ammonium salt solution；Alcohol is mixed with polyamic acid ammonium salt solution, obtains polyamic acid ammonium salt spinning solution；Polyamic acid ammonium salt spinning solution spinning is obtained into polyamic acid ammonium salt fiber；By polyamic acid ammonium salt fiber hot imidization, polyimides micrometer fibers are obtained.The polyimides micron fiber diameter is 1-5 microns, has the characteristics that high-intensitive and high-modulus.
Description
Technical field
The present invention relates to a kind of preparations of polymer electrostatic spinning nanofiber, more particularly it relates to Electrospinning Method
The method for preparing polyimides micrometer fibers, belongs to technical field of polymer materials.
Background technique
There are a large amount of nitrogenous five-ring heterocycles, phenyl ring, ehter bond, carbonyl bond and amido bond in polyimides macromolecular main chain,
In amido bond it is particularly important, and fragrant nuclear carbon is connected with oxygen with double bond and the conjugation of heteroaromatic, all effectively
It enhances in conjunction with energy, when radiation is most used for polyimide fiber, the absorbable radiation of molecule far is not enough to open on strand
Atom between covalent bond, just because of the presence of this molecular structure, so that polyimide fiber can be resistant to high radiation, resistance to height
Warm, resistant to chemical etching, strand is not easy to break, has preferable thermal stability and excellent mechanical mechanics property, in atomic energy
Industry, space environment, aerospace, national defense construction, novel building, rapid, ocean development, sports apparatus, new energy
The fields such as source, Environmental Industry and safety device have a good application prospect.
Polyimide fiber mainly uses the method for melt spinning or wet spinning to prepare at present, but uses dry-spinning, wet spinning
The fiber produced etc. traditional spinning process obtains sub-micron of the diameter less than 1 micron generally at 5-30 microns if necessary
Or nanofiber must just use special spining technology, electrostatic spinning rule be it is most simple at present, directly prepare this Asia
The method of micron or nanofiber.However, the diameter of ultra-fine micrometer fibers is 1-5 microns, prepared using electrostatic spinning as
Ultra-fine polyimides micrometer fibers will be extremely difficult.This is because the boiling point of solvent is higher in polyamic acid (PAA) spinning solution,
Not volatile, electrostatic spinning jet stream is not easy to solidify when running between the two poles of the earth, is obtained with liquid condition or semisolid in two interpolars
The traction in long period or path causes the diameter of fiber to be both less than 1 micron.Therefore, research and development Static Spinning method prepares polyimides
The method of micrometer fibers is of great significance.
Summary of the invention
The technical problem to be solved in the present invention is to provide the methods that Electrospinning Method prepares polyimides micrometer fibers.
In order to achieve the above-mentioned object of the invention, this invention takes following technical schemes:
The method that Electrospinning Method prepares polyimides micrometer fibers, comprising the following steps:
By the dissolution of polyamic acid ammonium salt with water, polyamic acid ammonium salt solution is obtained；
Alcohol is mixed with polyamic acid ammonium salt solution, obtains polyamic acid ammonium salt spinning solution；
Polyamic acid ammonium salt spinning solution electrostatic spinning is obtained into polyamic acid ammonium salt fiber；
By polyamic acid ammonium salt fiber hot imidization, polyimides micrometer fibers are obtained.
In one embodiment, the mass concentration of polyamic acid ammonium salt is 45- in the polyamic acid ammonium salt solution
65wt%.
In one embodiment, the mass concentration of polyamic acid ammonium salt is in the polyamic acid ammonium salt spinning solution
15-35wt%.
In one embodiment, the mass concentration of polyamic acid ammonium salt is in the polyamic acid ammonium salt spinning solution
20-30wt%.
In one embodiment, the polyamic acid ammonium salt is polyamic acid triethylamine.
In one embodiment, the alcohol is ethyl alcohol or methanol.
In one embodiment, voltage is 10~30kV when the electrostatic spinning；Spinning-nozzle is collected to opposite electrode
The distance of substrate is 15~25cm；Spinning flow velocity is 0.001~0.005mm/s.
In one embodiment, the temperature of the hot imidization is 200~450 DEG C.
It is another object of the present invention to provide the polyimides micrometer fibers that the method is prepared.
In one embodiment, the diameter of the polyimides micrometer fibers is 1-5 microns.
Compared with prior art, the invention has the benefit that
The present invention forms highly concentrated solution using polyamic acid ammonium salt and water, and polyamic acid ammonium salt solution is in gel
Then state is diluted highly concentrated polyamic acid ammonium salt solution with alcohol, solution viscosity is greatly lowered, and keep appropriate
Concentration, when can promote electrostatic spinning in this way in jet stream solvent quick volatilization, jet stream rapid curing, forming diameter is that 1-5 is micro-
The thick polyamic acid ammonium salt fiber of rice forms polyimides micrometer fibers through hot imidization after, the fiber have it is high-intensitive and
The features such as high-modulus.In addition, water-based polyamic acid salt (PAAS), is conducive to the protection of environment and guarantees the life of laboratory technician
Health；Moreover, the storage of the PAAS as PI presoma can more long；Furthermore the monomer of the PAAS of synthesis can be a variety of, have
Conducive to the polyimides micrometer fibers for preparing different requirements.So the method has both environmental protection, economic and flexible advantage.
The above-mentioned of the application and other features, aspects and advantages are more readily understood with reference to following detailed description.
Specific embodiment
Unless otherwise defined, all technologies used herein and scientific term have and the common skill of fields of the present invention
The normally understood identical meaning of art personnel.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ",
" 1-3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range be intended to include its end value and
All integers and score in the range.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. frequency of occurrence) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the quantity obviously refers to singular.
To solve the above-mentioned problems, the present invention provides the methods that Electrospinning Method prepares polyimides micrometer fibers, including with
Lower step:
By the dissolution of polyamic acid ammonium salt with water, polyamic acid ammonium salt solution is obtained；
Alcohol is mixed with polyamic acid ammonium salt solution, obtains polyamic acid ammonium salt spinning solution；
Polyamic acid ammonium salt spinning solution electrostatic spinning is obtained into polyamic acid ammonium salt fiber；
By polyamic acid ammonium salt fiber hot imidization, polyimides micrometer fibers are obtained.
Polyimides micrometer fibers of the present invention refer to that the diameter of fiber is 1-5 microns.
It is preferably carried out mode as the present invention, the mass concentration of polyamic acid ammonium salt in the polyamic acid ammonium salt solution
For 45-65wt%.
It is preferably carried out mode as the present invention, the quality of polyamic acid ammonium salt in the polyamic acid ammonium salt spinning solution
Concentration is 15-35wt%；It is highly preferred that the mass concentration of polyamic acid ammonium salt is in the polyamic acid ammonium salt spinning solution
20-30wt%.
Water of the present invention is deionized water.
It is preferably carried out mode as the present invention, the polyamic acid ammonium salt is polyamic acid triethylamine.
Polyamic acid triethylamine (PAAS):
The preparation method of polyamic acid triethylamine (PAAS) of the present invention:
(1) synthesis of polyamic acid (PAA): using DMAc as solvent, equimolar 4 are weighed, 4 '-diphenyldiamines (ODA)
With pyromellitic acid anhydride (PMDA), successively it is dissolved in the 250mL three-necked flask of N2 protection, the mechanic whirl-nett reaction at -5 DEG C
18h, polyamic acid (PAA) solution that synthesis mass fraction is 12wt%.
(2) into PAA solution, a certain amount of triethylamine (amount of substance slowly the preparation of polyamic acid salt (PAAS): is added dropwise
It is 1.5 times of-COOH in solution), mechanical stirring 5h at -5 DEG C prepares polyamic acid salt (PAAS).It is viscous that Ubbelohde viscometer surveys it
Degree is 2.3dL g-1。
Highly concentrated solution is formed in the dissolution of polyamic acid ammonium salt and water in the present invention, polyamic acid ammonium salt solution is solidifying in half
Then gluey state is diluted highly concentrated polyamic acid ammonium salt solution with alcohol, further decreases viscosity, but keep phase simultaneously
To high concentration, can promote electrostatic spinning in this way is the quick volatilization of solvent in jet stream, and jet stream rapid curing, forming diameter is
1-5 microns of thick polyamic acid ammonium salt fibers；The alcohol is absolute alcohol, is preferably carried out mode as the present invention, the alcohol is
Ethyl alcohol or methanol；It is highly preferred that the alcohol is methanol.
Mode is preferably carried out as the present invention, and voltage is 10~30kV when the electrostatic spinning；Spinning-nozzle is to opposed
The distance that electrode collects substrate is 15~25cm；Spinning flow velocity is 0.001~0.005mm/s.
It is preferably carried out mode as the present invention, the temperature of the hot imidization is 300~450 DEG C；It is highly preferred that described
The temperature of hot imidization is 380 DEG C.
It is another object of the present invention to provide the polyimides micrometer fibers that the method is prepared.
It is preferably carried out mode as the present invention, the diameter of the polyimides micrometer fibers is 1-5 microns.
The method that Electrospinning Method of the present invention prepares polyimides micrometer fibers is simple to operate, prepared polyamides
Imines micrometer fibers can be widely used in spacecraft, flexible cable, loomage, nuclear industry, composite material and fire protection flame retarding
The fields such as material.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of foregoing invention, still fall within protection scope of the present invention.
In addition, if illustrated without other, it is raw materials used to be all commercially available.
Embodiment 1
The polyamic acid ammonium salt for weighing 30g is dissolved in deionized water and stirs, and obtains the mass concentration of polyamic acid ammonium salt
For the polyamic acid ammonium salt solution of 45wt%；Methanol is added to polyamic acid ammonium salt solution to be diluted, stirs, obtains polyamide
The mass concentration of acid ammonium salt is the polyamic acid ammonium salt spinning solution of 15wt%；Polyamic acid ammonium salt spinning solution is passed through into electrostatic
When spinning prepares polyamic acid ammonium salt fiber, voltage, collection distance and flow velocity are respectively 13kV, 20cm and 0.002mm/s；With steel
Silk screen (90 mesh) collects polyamic acid ammonium salt fiber as supporter, is placed in vacuum drying oven, 70 DEG C of baking 6h, in high temperature furnace
380 DEG C of progress hot imidization processing are to get polyimides micrometer fibers.The diameter of polyimides micrometer fibers is 1-2 microns, is broken
Resistance to spalling is 3.55GPa, modulus 150.3GPa, elongation at break 3.6%.
Embodiment 2
The polyamic acid ammonium salt for weighing 30g is dissolved in deionized water and stirs, and obtains the mass concentration of polyamic acid ammonium salt
For the polyamic acid ammonium salt solution of 45wt%；Methanol is added to polyamic acid ammonium salt solution to be diluted, stirs, obtains polyamide
The mass concentration of acid ammonium salt is the polyamic acid ammonium salt spinning solution of 10wt%；Polyamic acid ammonium salt spinning solution is passed through into electrostatic
When spinning prepares polyamic acid ammonium salt fiber, voltage, collection distance and flow velocity are respectively 13kV, 20cm and 0.002mm/s；With steel
Silk screen (90 mesh) collects polyamic acid ammonium salt fiber as supporter, is placed in vacuum drying oven, 70 DEG C of baking 6h, in high temperature furnace
380 DEG C of progress hot imidization processing are to get polyimides micrometer fibers.The diameter of polyimides micrometer fibers is 2.5-3 microns,
Breaking strength is 3.7GPa, modulus 165.5GPa, elongation at break 3.3%.
Embodiment 3
The polyamic acid ammonium salt for weighing 30g is dissolved in deionized water and stirs, and obtains the mass concentration of polyamic acid ammonium salt
For the polyamic acid ammonium salt solution of 50wt%；Methanol is added to polyamic acid ammonium salt solution to be diluted, stirs, obtains polyamide
The mass concentration of acid ammonium salt is the polyamic acid ammonium salt spinning solution of 12wt%；Polyamic acid ammonium salt spinning solution is passed through into electrostatic
When spinning prepares polyamic acid ammonium salt fiber, voltage, collection distance and flow velocity are respectively 13kV, 20cm and 0.002mm/s；With steel
Silk screen (90 mesh) collects polyamic acid ammonium salt fiber as supporter, is placed in vacuum drying oven, 70 DEG C of baking 6h, in high temperature furnace
380 DEG C of progress hot imidization processing are to get polyimides micrometer fibers.The diameter of polyimides micrometer fibers is 3-4 microns, is broken
Resistance to spalling is 3.85GPa, modulus 170.5GPa, elongation at break 3.1%.
Embodiment 4
The polyamic acid ammonium salt for weighing 30g is dissolved in deionized water and stirs, and obtains the mass concentration of polyamic acid ammonium salt
For the polyamic acid ammonium salt solution of 50wt%；Methanol is added to polyamic acid ammonium salt solution to be diluted, stirs, obtains polyamide
The mass concentration of acid ammonium salt is the polyamic acid ammonium salt spinning solution of 8wt%；Polyamic acid ammonium salt spinning solution is passed through into electrostatic
When spinning prepares polyamic acid ammonium salt fiber, voltage, collection distance and flow velocity are respectively 13kV, 20cm and 0.002mm/s；With steel
Silk screen (90 mesh) collects polyamic acid ammonium salt fiber as supporter, is placed in vacuum drying oven, 70 DEG C of baking 6h, in high temperature furnace
380 DEG C of progress hot imidization processing are to get polyimides micrometer fibers.The diameter of polyimides micrometer fibers is 2-3 microns, is broken
Resistance to spalling is 4.1GPa, modulus 180GPa, elongation at break 3.2%.
Embodiment 5
The polyamic acid ammonium salt for weighing 30g is dissolved in deionized water and stirs, and obtains the mass concentration of polyamic acid ammonium salt
For the polyamic acid ammonium salt solution of 65wt%；Ethyl alcohol is added to polyamic acid ammonium salt solution to be diluted, stirs, obtains polyamide
The mass concentration of acid ammonium salt is the polyamic acid ammonium salt spinning solution of 14wt%；Polyamic acid ammonium salt spinning solution is passed through into electrostatic
When spinning prepares polyamic acid ammonium salt fiber, voltage, collection distance and flow velocity are respectively 13kV, 20cm and 0.002mm/s；With steel
Silk screen (90 mesh) collects polyamic acid ammonium salt fiber as supporter, is placed in vacuum drying oven, 70 DEG C of baking 6h, in high temperature furnace
380 DEG C of progress hot imidization processing are to get polyimides micrometer fibers.The diameter of polyimides micrometer fibers is 3-4.5 microns,
Breaking strength is 4.22GPa, modulus 200.5GPa, elongation at break 2.9%.
Embodiment 6
The polyamic acid ammonium salt for weighing 30g is dissolved in deionized water and stirs, and obtains the mass concentration of polyamic acid ammonium salt
For the polyamic acid ammonium salt solution of 65wt%；Methanol is added to polyamic acid ammonium salt solution to be diluted, stirs, obtains polyamide
The mass concentration of acid ammonium salt is the polyamic acid ammonium salt spinning solution of 16wt%；Polyamic acid ammonium salt spinning solution is passed through into electrostatic
When spinning prepares polyamic acid ammonium salt fiber, voltage, collection distance and flow velocity are respectively 13kV, 20cm and 0.002mm/s；With steel
Silk screen (90 mesh) collects polyamic acid ammonium salt fiber as supporter, is placed in vacuum drying oven, 70 DEG C of baking 6h, in high temperature furnace
380 DEG C of progress hot imidization processing are to get polyimides micrometer fibers.The diameter of polyimides micrometer fibers is 4-5 microns, is broken
Resistance to spalling is 4.36GPa, modulus 221.8GPa, elongation at break 2.6%.
Comparative example 1
The polyamic acid ammonium salt for weighing 30g is dissolved in deionized water and stirs, and obtains the mass concentration of polyamic acid ammonium salt
For the polyamic acid ammonium salt solution of 30wt%；Polyamic acid ammonium salt solution is prepared into polyamic acid ammonium salt fiber by electrostatic spinning
When, voltage, collection distance and flow velocity are respectively 13kV, 20cm and 0.002mm/s；It is collected using steel wire (90 mesh) as supporter
Polyamic acid ammonium salt fiber, is placed in vacuum drying oven, 70 DEG C of baking 6h, 380 DEG C of progress hot imidization processing in high temperature furnace, i.e.,
Obtain polyimides micrometer fibers.The diameter of polyimides micrometer fibers is 0.1-0.3 microns, breaking strength 1.3GPa, modulus
For 31.2GPa, elongation at break 8.9%.
Comparative example 2
The polyamic acid for weighing 30g is dissolved in deionized water and stirs, and the mass concentration for obtaining polyamic acid is 50wt%
Polyamic acid solution；Methanol is added to polyamic acid solution to be diluted, stirs, the mass concentration for obtaining polyamic acid is
The polyamic acid spinning solution of 30wt%；When polyamic acid spinning solution is prepared polyamic acid fiber by electrostatic spinning, electricity
Pressure, collection distance and flow velocity are respectively 13kV, 20cm and 0.002mm/s；Polyamides is collected using steel wire (90 mesh) as supporter
Amino acid fiber, is placed in vacuum drying oven, 70 DEG C of baking 6h, and 380 DEG C of progress hot imidization processing are in high temperature furnace to get polyamides Asia
Amine micrometer fibers.The diameter of polyimides micrometer fibers is 0.05-0.1 microns, breaking strength 1.0GPa, and modulus is
20.6GPa, elongation at break 10.6%.
Example above-mentioned is merely illustrative, some features of feature for explaining the present invention.The attached claims
It is intended to the range as wide as possible for requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combined selection embodiment explanation.Therefore, the purpose of applicant is that the attached claims are not illustrated the present invention
Feature exemplary selectional restriction.And the progress in science and technology will be formed language express it is inaccurate due to and not
The possible equivalent being presently considered or son replacement, and these variations should also be interpreted in the conceived case by appended
Claim covering.
Claims (5)
1. the method that Electrospinning Method prepares polyimides micrometer fibers, which comprises the following steps:
Polyamic acid ammonium salt is dissolved in the water, polyamic acid ammonium salt solution is obtained；
Alcohol is mixed with polyamic acid ammonium salt solution, obtains polyamic acid ammonium salt spinning solution；
Polyamic acid ammonium salt spinning solution electrostatic spinning is obtained into polyamic acid ammonium salt fiber；
By polyamic acid ammonium salt fiber hot imidization, polyimides micrometer fibers are obtained；
Wherein, the mass concentration of polyamic acid ammonium salt is 15-35wt% in the polyamic acid ammonium salt spinning solution；
The polyamic acid ammonium salt is polyamic acid triethylamine；
The alcohol is ethyl alcohol or methanol；
The diameter of the polyimides micrometer fibers is 1-5 microns.
2. the method that Electrospinning Method according to claim 1 prepares polyimides micrometer fibers, which is characterized in that the polyamides
The mass concentration of polyamic acid ammonium salt is 45-65% in amino acid ammonium salt solution.
3. the method that Electrospinning Method according to claim 1 prepares polyimides micrometer fibers, which is characterized in that the electrostatic
Voltage is 10~30kV when spinning；Spinning-nozzle collects the distance of substrate to opposite electrode as 15~25cm；Spinning flow velocity is
0.001~0.005mm/s.
4. the method that Electrospinning Method according to claim 1 prepares polyimides micrometer fibers, which is characterized in that the heat is sub-
The temperature of amination is 200~450 DEG C.
5. according to claim 1 to the polyimides micrometer fibers that any one of 4 the methods are prepared.
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