CN115125630A - Preparation method of irradiation-resistant polyimide fiber - Google Patents
Preparation method of irradiation-resistant polyimide fiber Download PDFInfo
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- CN115125630A CN115125630A CN202210883686.8A CN202210883686A CN115125630A CN 115125630 A CN115125630 A CN 115125630A CN 202210883686 A CN202210883686 A CN 202210883686A CN 115125630 A CN115125630 A CN 115125630A
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- 239000000835 fiber Substances 0.000 title claims abstract description 158
- 239000004642 Polyimide Substances 0.000 title claims abstract description 96
- 229920001721 polyimide Polymers 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000009987 spinning Methods 0.000 claims abstract description 71
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 49
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 78
- 229910052757 nitrogen Inorganic materials 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 26
- 239000003570 air Substances 0.000 claims description 25
- 238000002166 wet spinning Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 230000001112 coagulating effect Effects 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- -1 methylene, sulfonyl Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 abstract description 7
- FZEYVTFCMJSGMP-UHFFFAOYSA-N acridone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3NC2=C1 FZEYVTFCMJSGMP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 24
- 239000002002 slurry Substances 0.000 description 24
- 239000004952 Polyamide Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 22
- 229920002647 polyamide Polymers 0.000 description 22
- 238000012360 testing method Methods 0.000 description 14
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 9
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 5
- GDALETGZDYOOGB-UHFFFAOYSA-N Acridone Natural products C1=C(O)C=C2N(C)C3=CC=CC=C3C(=O)C2=C1O GDALETGZDYOOGB-UHFFFAOYSA-N 0.000 description 4
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
-
- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention provides a preparation method of irradiation-resistant polyimide fibers, which comprises the following steps: A) mixing aromatic dianhydride and aromatic diamine in a solvent, and carrying out polymerization reaction to obtain a polyamic acid spinning solution; B) spinning the polyamic acid spinning solution to obtain polyamic acid fiber; C) imidizing the polyamic acid fiber to obtain a polyimide fiber; according to the preparation method, the xanthone and acridone structures are introduced into the polyimide main chain, the novel polyimide fiber is prepared through a two-step method, the mechanical property, the service temperature and the irradiation resistance of the fiber are improved, and the preparation method is more suitable for being applied to the high-technology fields of aviation, nuclear power and the like.
Description
Technical Field
The invention relates to the technical field of high-performance organic fibers, in particular to a preparation method of an irradiation-resistant polyimide fiber.
Background
The polyimide fiber is an organic synthetic fiber with a molecular chain containing an imide ring, has excellent performances of high strength, high modulus, high and low temperature resistance, flame retardance and the like, comprises a composite material, a rope, a sheath, paper, a filter bag and the like, and is widely applied to the fields of national defense and military industry, high-temperature dust removal, warm-keeping clothes and the like. The factors influencing the performance of polyimide fibers mainly include monomer species, intermolecular interactions, rigidity and flexibility of chains, orientation, crystallinity and processing conditions.
The preparation method of the polyimide fiber can be divided into a one-step method and a two-step method according to different spinning solutions and reaction mechanisms. The one-step method comprises the steps of synthesizing a polyimide solution by adopting a high-boiling-point solvent at a high temperature of 180-220 ℃, and spinning to obtain polyimide fibers; the method can obtain the polyimide fiber with high molecular weight and high crystallinity, but the development and large-scale application of the polyimide fiber are severely restricted by the selection of soluble monomers and the use of toxic solvents; chinese patent ZL 02112048.X, US patent US 4,370,290, US 5,378,420 all disclose the preparation of polyimide fibers in one step. The two-step method is that diamine and dianhydride react in polar aprotic solvent to generate polyamic acid solution, the polyamic acid solution is sprayed into a coagulating bath to obtain polyamic acid fiber, and then polyimide fiber is obtained through imidization and hot drawing processes; the method has the advantages of wide monomer selectivity, low solvent toxicity, capability of integrated continuous spinning and the like; chinese patents CN101338462B, CN112695402A, CN105297166B, CN105671680B and CN105237547B all disclose two-step methods for preparing polyimide fibers.
Polyimide fibers are widely used in various high-tech fields as high-performance organic fibers. With the progress of science and technology, the use environment of materials is severer, higher requirements are put forward on the performance of polyimide, and the polyimide fiber is found in the application process of high-orbit spacecraft, the high-energy ultraviolet and space ray irradiation environment can accelerate the degradation and aging of the polyimide fiber, the performance and the service life of the fiber are seriously influenced, and the polyimide fiber is required to have more excellent irradiation resistance. Radiation resistant polyimide fibers have been less studied and have limited options for monomers and methods.
Disclosure of Invention
The invention aims to provide a preparation method of polyimide fibers, and the polyimide fibers prepared by the method have high mechanical property, high use temperature and high irradiation resistance.
The application also provides a preparation method of the radiation-resistant polyimide fiber, which comprises the following steps:
A) mixing aromatic dianhydride and aromatic diamine in a solvent, and carrying out polymerization reaction to obtain a polyamic acid spinning solution;
B) spinning the polyamic acid spinning solution to obtain polyamic acid fiber;
C) imidizing the polyamic acid fiber to obtain a polyimide fiber;
the aromatic dianhydride is selected from one or more of formula (I1), formula (I2) and formula (I3);
the aromatic diamine is selected from one or more of formula (II 1), formula (II 2), formula (II 3), formula (II 4), formula (II 5), formula (II 6) and formula (II 7);
wherein A is selected from O, S, carbonyl,
R is selected from O, S, methylene, sulfonyl, carbonyl, pyridyl or a group containing two N on a benzene ring;
d is selected from O, S or N.
Preferably, the molar ratio of the aromatic dianhydride to the aromatic diamine is 0.9: 1-1: 0.9, and the solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
Preferably, the solid content of the polyamic acid in the polyamic acid spinning solution is 5-40 wt%, the temperature of the polymerization reaction is-10-50 ℃, and the time is 5-72 h.
Preferably, the spinning is dry-jet wet spinning or wet spinning;
the dry-jet wet spinning method comprises the following specific steps: sequentially filtering and defoaming the polyamic acid spinning solution in vacuum, extruding the polyamic acid spinning solution from a spinneret orifice through a metering pump, and sequentially performing coagulating bath forming, washing and drying after passing through an air layer to obtain polyamic acid fiber;
the wet spinning method comprises the following specific steps: and sequentially filtering and defoaming the polyamic acid spinning solution in vacuum, extruding the polyamic acid spinning solution from a spinneret orifice through a metering pump, and finally sequentially carrying out coagulating bath forming, washing and drying to obtain the polyamic acid fiber.
Preferably, in the process of spinning by a dry-jet wet method, the coagulating bath is a mixture of one of methanol, ethanol, ethylene glycol, butanol, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone and water, the height of the air layer is 3-100 mm, the aperture of the spinneret orifice is phi 0.05-phi 0.2mm, the number of the spinneret orifice is 20-1000 holes, the spray-draw ratio is 1.0-7.0 times, and the speed is 5-100 m/min;
in the wet spinning process, the coagulating bath is a mixture of water and one of methanol, ethanol, ethylene glycol, butanol, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, the aperture of each spinneret orifice is phi 0.04-phi 0.15mm, the number of the spinneret orifices is 30-12000, the spray-draw ratio is 1.0-5.0 times, and the speed is 5-100 m/min.
Preferably, the imidization temperature is gradient heating, the gradient heating temperature is 50-500 ℃, the heating rate is 1-30 ℃/min, and the atmosphere of the gradient heating is air, nitrogen or argon.
Preferably, the imidization further comprises:
the imidized as-spun fibers are subjected to hot drawing.
Preferably, the hot drawing temperature is 300-600 ℃, the drawing ratio is 1.0-5.0, and the atmosphere is inert atmosphere.
The application provides a preparation method of polyimide fiber, which comprises the steps of polymerizing specific diamine and dianhydride monomers to prepare polyamide acid spinning solution, spinning to prepare polyamide acid fiber, drying the polyamide acid fiber, and performing thermal imidization to obtain the polyimide fiber. The invention introduces xanthone and acridone structures into a polyimide molecular chain, and improves the mechanical property, the use temperature and the irradiation resistance of the polyimide fiber. The experimental results show that: the polyimide fiber prepared by the method has the breaking strength of 1-4 GPa, and the strength retention rate after irradiation is more than 85%.
Drawings
FIG. 1 is a FT-IR spectrum of a polyimide fiber prepared in example 1 of the present invention;
FIG. 2 is a DMA curve of a polyimide fiber prepared in example 1 of the present invention;
FIG. 3 TGA curve of a polyimide fiber prepared according to example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the requirement of radiation resistance of polyimide fibers in the prior art, the structure of xanthone and acridone is introduced into a polyimide main chain, the novel polyimide fiber is prepared by a two-step method, the mechanical property, the use temperature and the radiation resistance of the fiber are improved, and the novel polyimide fiber is more suitable for being applied to the high-technology fields of aviation, nuclear power and the like. Specifically, the invention provides a preparation method of radiation-resistant polyimide fibers, which comprises the following steps:
A) mixing aromatic dianhydride and aromatic diamine in a solvent, and carrying out polymerization reaction to obtain a polyamic acid spinning solution;
B) spinning the polyamic acid spinning solution to obtain polyamic acid fiber;
C) imidizing the polyamic acid fiber to obtain polyimide fiber;
the aromatic dianhydride is selected from one or more of formula (I1), formula (I2) and formula (I3);
the aromatic diamine is selected from one or more of formula (II 1), formula (II 2), formula (II 3), formula (II 4), formula (II 5), formula (II 6) and formula (II 7);
wherein A is selected from O, S, carbonyl,
R is selected from O, S, methylene, sulfonyl, carbonyl, pyridyl or a group containing two N on a benzene ring;
d is selected from O, S or N.
The preparation method of the radiation-resistant polyimide fiber provided by the application comprises the following four steps: preparing a polyamic acid spinning solution, preparing a polyamic acid fiber, imidizing the polyamic acid fiber and hot drawing the polyimide fiber; in the steps, specific dianhydride and diamine monomers are introduced, and a xanthone structure and an acridone structure are introduced into a polyimide molecular chain, so that the mechanical property, the use temperature and the irradiation resistance of the polyimide fiber are improved.
Specifically, in the preparation process, firstly, a polyamic acid spinning solution is prepared, wherein aromatic dianhydride and aromatic diamine are mixed in a solvent, and the polyamic acid spinning solution is obtained after polymerization reaction; in this process the aromatic dianhydride is specifically selected from the following structures and the aromatic diamine is specifically selected from the following structures:
in a specific embodiment, the aromatic dianhydride is selected from one or two of biphenyl tetracarboxylic dianhydride and pyromellitic dianhydride, and the aromatic diamine is specifically selected from the following combinations: p-phenylenediamine and meta-xanthone diamine, 4' -diaminodiphenyl ether and meta-xanthone diamine, 2- (4-aminophenyl) -5-aminobenzimidazole and para-xanthone diamine, p-phenylenediamine and para-xanthone diamine, p-phenylenediamine and acridone diamine. Specifically, the molar ratio of the aromatic dianhydride to the aromatic diamine is 0.9:1 to 1:0.9, and more specifically, the molar ratio of the aromatic dianhydride to the aromatic diamine is 1: 1. The solvent is specifically selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone. The solid content of the polyamic acid in the polyamic acid spinning solution is 5-40 wt%, the temperature of the polymerization reaction is-10-50 ℃, and the time is 5-72 hours; more specifically, the temperature of the polymerization reaction is 0-20 ℃, and the time of the polymerization reaction is 12-24 h.
Spinning the polyamic acid spinning solution to obtain polyamic acid fiber; in the process, the spinning is carried out according to a method well known to a person skilled in the art, and specifically, the spinning can be carried out by a dry-jet wet spinning method or a wet spinning method; more specifically, the dry-jet wet spinning is as follows: sequentially filtering and defoaming the polyamic acid spinning solution in vacuum, extruding the polyamic acid spinning solution from a spinneret orifice through a metering pump, and sequentially performing coagulating bath forming, washing and drying after passing through an air layer to obtain polyamic acid fiber;
the wet spinning method comprises the following specific steps: and sequentially filtering and defoaming the polyamic acid spinning solution in vacuum, extruding the polyamic acid spinning solution from a spinneret orifice through a metering pump, and finally sequentially carrying out coagulating bath forming, washing and drying to obtain the polyamic acid fiber.
In the process of the dry-jet wet spinning, the coagulating bath is a mixture of one of methanol, ethanol, ethylene glycol, butanol, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone and water, the height of the air layer is 3-100 mm, the aperture of each spinneret orifice is phi 0.05-phi 0.2mm, the number of the spinneret orifices is 50-400, the jet-draw ratio is 1.0-7.0 times, and the speed is 5-100 m/min; specifically, the height of air bed is 10 ~ 30 mm. The diameter of the spinneret orifice is phi 0.10-phi 0.15mm, the number of the spinneret orifices is 20-1000, the spray-draw ratio is 2.0-4.0 times, and the speed is 20-60 m/min.
In the wet spinning process, the coagulating bath is a mixture of water and one of methanol, ethanol, ethylene glycol, butanol, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, the aperture of each spinneret orifice is phi 0.04-phi 0.15mm, the number of the spinneret orifices is 30-12000, the spray-draw ratio is 1.0-5.0 times, and the speed is 5-100 m/min; specifically, the diameter of the spinneret orifice is phi 0.08-phi 0.12mm, the number of the spinneret orifices is 100-10000, the spray-draw ratio is 1.5-4.0 times, and the speed is 20-60 m/min.
Then, imidizing the obtained polyamic acid fiber to obtain a polyimide fiber; in the imidization process, a gradient heating mode is adopted, wherein the temperature of the gradient heating is 50-500 ℃, the heating rate is 1-30 ℃/min, and the atmosphere of the gradient heating is air, nitrogen or argon; more specifically, the temperature of the imidization is 50-400 ℃, and the temperature rise speed is 5-20 ℃/min.
The application finally carries out hot drawing on the obtained nascent fiber so as to enable the polyimide fiber to have better mechanical property. The temperature of the hot drawing is 300-600 ℃, the drawing multiplying power is 1.0-5.0, and the atmosphere is inert atmosphere; more specifically, the hot drawing temperature is 450-580 ℃, the drawing multiplying power is 1.2-2.0, and the atmosphere is nitrogen or argon.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method of the radiation-resistant polyimide fiber provided by the present invention, and the scope of the present invention is not limited by the following examples.
The mechanical properties of the fibers are tested by adopting a Textech FAVIMAT single fiber tensile strength tester, the tensile speed is 5mm/min, the initial modulus is the modulus in the interval of 0.2-0.4% of strain in a stress-strain curve, at least 10 samples are tested for each group of fibers, and the arithmetic mean value is taken.
Example 1
Adding 294.22g (1.0mol) of biphenyltetracarboxylic dianhydride, 97.33g (0.9mol) of p-phenylenediamine, 22.62g (0.1mol) of m-xanthenediamine and 2347g of N, N-dimethylacetamide (DMAc) into a three-neck round-bottom flask which is provided with a mechanical stirrer and is protected by nitrogen, reacting for 24 hours at 0 ℃ to obtain a light yellow polyamic acid solution, and filtering the solution to be directly used as spinning slurry;
the polyamic acid slurry is spun and formed by adopting a dry-jet wet spinning technical route, the normal-temperature spinning slurry is accurately metered by a metering pump, and the spinning slurry is extruded out from a spinneret orifice and enters a coagulating bath of N, N-dimethylacetamide and water (the volume ratio is 1: 2) through an air layer; the spinneret plate has 50 holes, the aperture phi is 0.14mm, the spray-draw ratio is 4 times, the spinning speed is 50m/min, and the height of an air layer is 10 mm; washing the nascent fiber with water, and drying by a hot nitrogen channel to obtain polyamide acid fiber;
treating the polyamide acid fiber in a nitrogen environment by a gradient heating thermal imidization furnace to obtain the polyimide fiber, wherein the thermal imidization temperature is 50-380 ℃, and the heating speed is 10 ℃/min; the obtained polyimide fiber is drafted by 1.5 times at 500 ℃ in a nitrogen environment to obtain the polyimide finished product fiber.
According to the method of the technical scheme, the mechanical property of the polyimide fiber prepared in the embodiment 1 of the invention is tested, and the test result is as follows: the breaking strength of the fiber is 1.7GPa, the modulus is 85.3GPa, and the breaking elongation is 2.7%.
Example 2
218.12g (1.0mol) of pyromellitic dianhydride, 140.17g (0.7mol) of 4, 4' -diaminodiphenyl ether, 67.87g (0.3mol) of meta-xanthone diamine and 2850g of N, N-dimethylacetamide (DMAc) are added into a three-necked round-bottomed flask equipped with mechanical stirring and protected by nitrogen, and reacted at 10 ℃ for 12 hours to obtain a pale yellow polyamic acid solution which is directly used as spinning dope after being filtered;
the polyamide acid slurry is spun and formed by adopting a dry-jet wet spinning technical route, the normal-temperature spinning slurry is accurately metered by a metering pump, and then is extruded out of a spinneret orifice and enters a coagulating bath of N, N-dimethylacetamide and water (1: 3 volume ratio) through an air layer, the spinneret plate is 50 holes, the aperture phi is 0.12mm, the jet-draw ratio is 3 times, the spinning speed is 50m/min, and the height of the air layer is 10 mm; washing the nascent fiber with water, and drying by a hot nitrogen channel to obtain polyamide acid fiber;
treating the polyamide acid fiber in a nitrogen environment by a gradient heating thermal imidization furnace to obtain the polyimide fiber, wherein the thermal imidization temperature is 50-430 ℃, and the heating speed is 5 ℃/min; the obtained polyimide fiber is drafted by 1.75 times at 500 ℃ in a nitrogen environment to obtain the polyimide finished product fiber.
According to the method of the technical scheme, the mechanical property of the polyimide fiber prepared in the embodiment 2 of the invention is tested, and the test result is as follows: the breaking strength of the fiber is 1.1GPa, the modulus is 22.6GPa, and the breaking elongation is 4.9%.
Example 3
A three-necked round-bottomed flask equipped with mechanical stirring and nitrogen blanket was charged with 294.22g (1.0mol) of biphenyltetracarboxylic dianhydride, 112.13g (0.5mol) of 2- (4-aminophenyl) -5-aminobenzimidazole, 113.12g (0.5mol) of p-xanthone diamine, 3815g of N, N-Dimethylformamide (DMF), reacted at 0 ℃ for 48 hours to give a pale yellow polyamic acid solution, which was filtered and used as a spinning dope directly;
the polyamide acid slurry is spun and formed by adopting a dry-jet wet spinning technical route, the normal-temperature spinning slurry is accurately metered by a metering pump, the spinning slurry is extruded from a spinneret orifice and enters a coagulating bath of N, N-dimethylformamide and water (1: 2 volume ratio) through an air layer, the spinneret plate is 50 holes, the aperture phi is 0.14mm, the jet-draw ratio is 3 times, the spinning speed is 40m/min, and the height of the air layer is 10 mm; washing the nascent fiber with water, and drying by a hot nitrogen channel to obtain polyamide acid fiber;
treating the polyamide acid fiber in a nitrogen environment by a gradient heating thermal imidization furnace to obtain the polyimide fiber, wherein the thermal imidization temperature is 50-500 ℃, and the heating speed is 10 ℃/min; the obtained polyimide fiber is drafted by 2.0 times at 530 ℃ in a nitrogen environment to obtain the polyimide finished product fiber.
According to the method of the technical scheme, the mechanical property of the polyimide fiber prepared in the embodiment 3 of the invention is tested, and the test result is as follows: the breaking strength of the fiber is 3.7GPa, the modulus is 102.5GPa, and the breaking elongation is 2.1%.
Example 4
294.22g (1.0mol) of biphenyltetracarboxylic dianhydride, 75.70g (0.7mol) of p-phenylenediamine, 67.87g (0.3mol) of p-xanthenediamine and 2481g of N, N-Dimethylformamide (DMF) are added into a three-neck round-bottom flask which is provided with a mechanical stirrer and protected by nitrogen, and reacted for 48 hours at 5 ℃ to obtain a light yellow polyamic acid solution which is directly used as spinning slurry after being filtered;
the polyamic acid slurry is spun and formed by adopting a dry-jet wet spinning technical route, the normal-temperature spinning slurry is accurately metered by a metering pump, and then is extruded out of a spinneret orifice and enters a coagulating bath of N, N-dimethylformamide and water (1: 4 volume ratio) through an air layer, the spinneret plate is 100 holes, the aperture phi is 0.16mm, the jet-draw ratio is 3 times, the spinning speed is 40m/min, and the height of the air layer is 10 mm; washing the nascent fiber with water, and drying by a hot nitrogen channel to obtain polyamide acid fiber;
and treating the polyamide acid fiber in a nitrogen environment by a gradient heating thermal imidization furnace to obtain the polyimide fiber. The thermal imidization temperature is 50-400 ℃, and the heating rate is 20 ℃/min; the obtained polyimide fiber is drafted by 1.75 times at 550 ℃ in a nitrogen environment to obtain the polyimide finished product fiber.
According to the method of the technical scheme, the mechanical property of the polyimide fiber prepared in the embodiment 4 of the invention is tested, and the test result is as follows: the breaking strength of the fiber is 2.5GPa, the modulus is 96.8GPa, and the breaking elongation is 5.1%.
Example 5
147.11g (0.5mol) of biphenyl tetracid dianhydride, 109.06g (0.5mol) of pyromellitic dianhydride, 226.24g (1mol) of para-xanthone diamine and 2734g of N-methylpyrrolidone (NMP) are added into a three-neck round-bottom flask which is provided with mechanical stirring and protected by nitrogen, and react for 24 hours at the temperature of-10 ℃ to obtain a light yellow polyamic acid solution which is directly used as spinning slurry after being filtered;
the polyamic acid slurry is spun and formed by adopting a dry-jet wet spinning technical route, the normal-temperature spinning slurry is accurately metered by a metering pump, and then is extruded out of a spinneret orifice and enters a coagulating bath of N-methyl pyrrolidone and water (1: 5 volume ratio) through an air layer, the spinneret plate is 200 holes, the aperture phi is 0.12mm, the jet-draw ratio is 2.5 times, the spinning speed is 50m/min, and the height of the air layer is 15 mm; washing the nascent fiber with water, and drying by a hot nitrogen channel to obtain polyamide acid fiber;
treating the polyamide acid fiber in a nitrogen environment by a gradient heating thermal imidization furnace to obtain the polyimide fiber, wherein the thermal imidization temperature is 50-400 ℃, and the heating speed is 10 ℃/min; the obtained polyimide fiber is drafted by 1.5 times at 500 ℃ in a nitrogen environment to obtain the polyimide finished product fiber.
According to the method of the technical scheme, the mechanical property of the polyimide fiber prepared in the embodiment 5 of the invention is tested, and the test result is as follows: the breaking strength of the fiber is 1.2GPa, the modulus is 47.6GPa, and the breaking elongation is 3.3%.
Example 6
Into a three-necked round-bottomed flask equipped with mechanical stirring and protected with nitrogen gas were charged 218.12g (1.0mol) of pyromellitic dianhydride, 54.07g (0.5mol) of p-phenylenediamine, 112.63g (0.5mol) of acridone diamine, 2810g of N, N-dimethylacetamide (DMAc) at-10 ℃ for 24 hours to obtain a pale yellow polyamic acid solution, which was filtered and used as a spinning dope directly;
the polyamic acid slurry is spun and formed by adopting a dry-jet wet spinning technical route, the normal-temperature spinning slurry is accurately metered by a metering pump, and then is extruded out of a spinneret orifice and enters a coagulating bath of N, N-dimethylacetamide and water (1: 3 volume ratio) through an air layer, the spinneret plate is 400 holes, the aperture phi is 0.14mm, the jet-draw ratio is 4 times, the spinning speed is 50m/min, and the height of the air layer is 10 mm; washing the nascent fiber with water, and drying by a hot nitrogen channel to obtain polyamide acid fiber;
treating the polyamide acid fiber in a nitrogen environment by a gradient heating thermal imidization furnace to obtain the polyimide fiber, wherein the thermal imidization temperature is 50-430 ℃, and the heating speed is 10 ℃/min; the obtained polyimide fiber is drafted by 1.25 times at 500 ℃ in a nitrogen environment to obtain the polyimide finished product fiber.
According to the method of the technical scheme, the mechanical property of the polyimide fiber prepared in the embodiment 6 of the invention is tested, and the test result is as follows: the breaking strength of the fiber is 1.1GPa, the modulus is 33.2GPa, and the breaking elongation is 4.9%.
Example 7
A three-necked round-bottomed flask equipped with mechanical stirring and nitrogen blanket was charged with 294.22g (1.0mol) of biphenyltetracarboxylic dianhydride, 75.70g (0.7mol) of p-phenylenediamine, 67.58g (0.3mol) of acridone diamine, 2480g of N, N-dimethylacetamide (DMAc), and reacted at 0 ℃ for 24 hours to give a pale yellow polyamic acid solution, which was filtered and used directly as a spinning dope;
the polyamide acid slurry is spun and formed by adopting a dry-jet wet spinning technical route, the normal-temperature spinning slurry is accurately metered by a metering pump, and then is extruded out of a spinneret orifice and enters a coagulating bath of N, N-dimethylacetamide and water (1: 2 volume ratio) through an air layer, the spinneret plate is 50 holes, the aperture phi is 0.12mm, the jet-draw ratio is 4 times, the spinning speed is 50m/min, and the height of the air layer is 10 mm; washing the nascent fiber with water, and drying by a hot nitrogen channel to obtain polyamide acid fiber;
treating the polyamide acid fiber in a nitrogen environment by a gradient heating thermal imidization furnace to obtain the polyimide fiber, wherein the thermal imidization temperature is 50-430 ℃, and the heating speed is 10 ℃/min; drafting the obtained polyimide fiber at 530 ℃ for 2.0 times under a nitrogen environment to obtain a polyimide finished product fiber;
according to the method of the technical scheme, the mechanical properties of the polyimide fiber prepared in the embodiment 7 of the invention are tested, and the test result is as follows: the breaking strength of the fiber is 2.7GPa, the modulus is 77.0GPa, and the breaking elongation is 5.8%.
Example 8
A three-necked round-bottomed flask equipped with mechanical stirring and nitrogen protection was charged with 294.22g (1.0mol) of biphenyltetracarboxylic dianhydride, 64.88g (0.6mol) of p-phenylenediamine, 90.49g (0.4mol) of meta-xanthone diamine, 2761g of N, N-Dimethylformamide (DMF), and reacted at 10 ℃ for 48 hours to give a pale yellow polyamic acid solution which was directly used as a spinning dope after filtration;
the polyamic acid slurry is spun and formed by adopting a wet spinning technical route, the spinning slurry at normal temperature is accurately metered by a metering pump, and then is extruded from a spinneret orifice and enters a coagulating bath of N, N-dimethylformamide and water (1: 5 volume ratio), the spinneret orifice is 400 holes, the aperture phi is 0.12mm, the spray-draw ratio is 3.5 times, and the spinning speed is 60 m/min; washing the nascent fiber with water, and drying by a hot nitrogen channel to obtain polyamide acid fiber;
and treating the polyamide acid fiber in a nitrogen environment by a gradient heating thermal imidization furnace to obtain the polyimide fiber. The thermal imidization temperature is 50-400 ℃, and the heating rate is 10 ℃/min; the obtained polyimide fiber is drafted by 2.0 times at 510 ℃ in a nitrogen environment to obtain the polyimide finished product fiber.
According to the method of the technical scheme, the mechanical property of the polyimide fiber prepared in the embodiment 8 of the invention is tested, and the test result is as follows: the breaking strength of the fiber is 1.7GPa, the modulus is 51.5GPa, and the breaking elongation is 3.6%.
Comparative example 1
A three-necked round-bottomed flask equipped with mechanical stirring and nitrogen protection was charged with 294.22g (1.0mol) of biphenyltetracarboxylic dianhydride, 108.14g (1.0mol) of p-phenylenediamine, 2280g of N, N-dimethylacetamide (DMAc) and reacted at 0 ℃ for 24 hours to obtain a pale yellow polyamic acid solution which was directly used as a spinning dope after filtration;
the polyamic acid slurry was spun, heat imidized, and heat drawn to obtain polyimide fibers in the same manner as in example 1.
According to the method of the technical scheme, the mechanical property of the polyimide fiber prepared in the comparative example 1 of the invention is tested, and the test result is as follows: the breaking strength of the fiber is 1.0GPa, the modulus is 88.9GPa, and the breaking elongation is 1.7 percent.
Comparative example 2
Into a three-necked round-bottomed flask equipped with mechanical stirring and nitrogen blanket was added 218.12g (1.0mol) of pyromellitic dianhydride, 200.24g (1.0mol) of 4, 4' -diaminodiphenyl ether, 2030g of N, N-dimethylacetamide (DMAc), and reacted at 10 ℃ for 12 hours to obtain a pale yellow polyamic acid solution, which was directly used as a spinning dope after filtration;
the polyamic acid slurry was spun, heat imidized, and heat drawn to obtain polyimide fibers in the same manner as in example 2.
According to the method of the technical scheme, the mechanical properties of the polyimide fiber prepared by the comparative example 2 are tested, and the test result shows that the fiber has the breaking strength of 0.7GPa, the modulus of 9.6GPa and the breaking elongation of 8.2 percent.
Comparative example 3
To a three-necked round-bottomed flask equipped with mechanical stirring and nitrogen blanket was added 294.22g (1.0mol) of biphenyltetracarboxylic dianhydride, 224.26g (1.0mol) of 2- (4-aminophenyl) -5-aminobenzimidazole, 2938g of N, N-Dimethylformamide (DMF), and reacted at 0 ℃ for 48 hours to give a pale yellow polyamic acid solution, which was filtered and used as a spinning dope directly;
the polyamic acid slurry was spun, heat imidized, and heat drawn to obtain polyimide fibers in the same manner as in example 3.
According to the method of the technical scheme, the mechanical properties of the polyimide fiber prepared by the comparative example 3 are tested, and the test result shows that the fiber has the breaking strength of 1.7GPa, the modulus of 52.8GPa and the breaking elongation of 3.1%.
The polyimide fibers obtained in examples 1 to 8 and comparative examples 1 to 3 were subjected to the ultraviolet ray irradiation test, and the results are shown in Table 1, wherein Table 1 shows the results of the fiber breaking strength test before and after the ultraviolet ray irradiation, and the ultraviolet ray irradiation strength is 10.43w/m 2 The wavelength range is 280-315 nm.
TABLE 1 test results of polyimide fiber breaking strength before and after ultraviolet irradiation
FIG. 1 is a FT-IR spectrum of a polyimide fiber prepared in example 1, and FIG. 2 isDMA curve of polyimide fiber prepared in example 1, and TGA curve of polyimide fiber prepared in example 1 is shown in fig. 3. As can be seen in FIG. 1, 1772, 1701, 1352cm -1 Obvious characteristic peaks exist and respectively belong to an antisymmetric stretching vibration peak, a symmetric stretching vibration peak and a C-N stretching vibration peak of the imine cyclocarbonyl, which indicates that the polyimide fiber is successfully synthesized. As can be seen in fig. 2, the glass transition temperature of the polyimide fiber prepared in example 1 is 322 ℃. As can be seen in FIG. 3, the prepared polyimide fiber had 5 wt% thermal decomposition temperatures of 609 ℃ and 575 ℃ in nitrogen and air atmospheres, respectively.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A preparation method of radiation-resistant polyimide fibers comprises the following steps:
A) mixing aromatic dianhydride and aromatic diamine in a solvent, and carrying out polymerization reaction to obtain a polyamic acid spinning solution;
B) spinning the polyamic acid spinning solution to obtain polyamic acid fiber;
C) imidizing the polyamic acid fiber to obtain a polyimide fiber;
the aromatic dianhydride is selected from one or more of formula (I1), formula (I2) and formula (I3);
the aromatic diamine is selected from one or more of formula (II 1), formula (II 2), formula (II 3), formula (II 4), formula (II 5), formula (II 6) and formula (II 7);
wherein A is selected from O, S, carbonyl,
R is selected from O, S, methylene, sulfonyl, carbonyl, pyridyl or a group containing two N on a benzene ring;
d is selected from O, S or N.
2. The method according to claim 1, wherein the molar ratio of the aromatic dianhydride to the aromatic diamine is 0.9:1 to 1:0.9, and the solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.
3. The method according to claim 1, wherein the polyamic acid spinning solution has a solid content of polyamic acid of 5-40 wt%, and the polymerization temperature is-10-50 ℃ and the polymerization time is 5-72 h.
4. The production method according to claim 1, wherein the spinning is dry-jet wet spinning or wet spinning;
the dry-jet wet spinning method comprises the following specific steps: sequentially filtering and vacuum defoaming the polyamic acid spinning solution, extruding the polyamic acid spinning solution from a spinneret orifice through a metering pump, and sequentially performing coagulating bath forming, washing and drying after passing through an air layer to obtain polyamic acid fiber;
the wet spinning method comprises the following specific steps: and sequentially filtering and defoaming the polyamic acid spinning solution in vacuum, extruding the polyamic acid spinning solution from a spinneret orifice through a metering pump, and finally sequentially carrying out coagulating bath forming, washing and drying to obtain the polyamic acid fiber.
5. The preparation method according to claim 4, wherein in the dry-jet wet spinning process, the coagulating bath is a mixture of water and one of methanol, ethanol, ethylene glycol, butanol, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, the height of the air layer is 3-100 mm, the diameter of the spinneret hole is phi 0.05-phi 0.2mm, the number of the holes is 20-1000, the spray-draw ratio is 1.0-7.0 times, and the speed is 5-100 m/min;
in the wet spinning process, the coagulating bath is a mixture of water and one of methanol, ethanol, ethylene glycol, butanol, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, the aperture of each spinneret orifice is phi 0.04-phi 0.15mm, the number of the spinneret orifices is 30-12000, the spray-draw ratio is 1.0-5.0 times, and the speed is 5-100 m/min.
6. The method according to claim 1, wherein the imidization temperature is a temperature gradient, the temperature gradient is 50 to 500 ℃, the temperature rate is 1 to 30 ℃/min, and the atmosphere of the temperature gradient is air, nitrogen or argon.
7. The method according to claim 1, further comprising, after the imidizing:
the imidized as-spun fibers are subjected to hot drawing.
8. The method according to claim 7, wherein the hot drawing temperature is 300 to 600 ℃, the draw ratio is 1.0 to 5.0, and the atmosphere is an inert atmosphere.
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