CN115125630B - Preparation method of radiation-resistant polyimide fiber - Google Patents
Preparation method of radiation-resistant polyimide fiber Download PDFInfo
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- CN115125630B CN115125630B CN202210883686.8A CN202210883686A CN115125630B CN 115125630 B CN115125630 B CN 115125630B CN 202210883686 A CN202210883686 A CN 202210883686A CN 115125630 B CN115125630 B CN 115125630B
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- 239000000835 fiber Substances 0.000 title claims abstract description 165
- 239000004642 Polyimide Substances 0.000 title claims abstract description 95
- 229920001721 polyimide Polymers 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000005855 radiation Effects 0.000 title claims abstract description 9
- 238000009987 spinning Methods 0.000 claims abstract description 79
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 40
- 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 25
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- GDALETGZDYOOGB-UHFFFAOYSA-N Acridone Natural products C1=C(O)C=C2N(C)C3=CC=CC=C3C(=O)C2=C1O GDALETGZDYOOGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 73
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 27
- 239000004952 Polyamide Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 26
- 229920002647 polyamide Polymers 0.000 claims description 26
- 238000002166 wet spinning Methods 0.000 claims description 26
- 239000003570 air Substances 0.000 claims description 23
- 230000001112 coagulating effect Effects 0.000 claims description 20
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 239000000203 mixture Substances 0.000 claims description 11
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- -1 acridone diamine Chemical class 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 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 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims 1
- 238000005345 coagulation 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 8
- FZEYVTFCMJSGMP-UHFFFAOYSA-N acridone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3NC2=C1 FZEYVTFCMJSGMP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 15
- 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
- 238000010907 mechanical stirring Methods 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 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
- 230000006978 adaptation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000004076 pyridyl group Chemical group 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
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 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
- 239000000428 dust Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 125000000879 imine group Chemical group 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-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
- 238000011160 research Methods 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
- 238000009281 ultraviolet germicidal irradiation 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
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The application 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 obtaining a polyamic acid spinning solution after polymerization reaction; 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 application, the structure of xanthone and acridone is introduced into a polyimide main chain, and the novel polyimide fiber is prepared by a two-step method, so that the mechanical property, the use temperature and the irradiation resistance of the fiber are improved, and the novel polyimide fiber is more suitable for being applied to the high-tech fields of aviation, nuclear power and the like.
Description
Technical Field
The application 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 an imide ring in a molecular chain, has excellent performances of high strength, high modulus, high and low temperature resistance, flame retardance and the like, and the product 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, thermal clothing and the like. The factors influencing the properties of polyimide fibers mainly comprise monomer types, intermolecular interactions, rigid and flexible chains, orientation, crystallinity and processing conditions.
The preparation method of polyimide fibers can be classified into one-step and two-step methods according to the spinning solution and the reaction mechanism. Wherein, the one-step method is to synthesize polyimide solution by adopting a high boiling point solvent at a high temperature of 180-220 ℃ and obtain polyimide fiber after spinning; the method can obtain polyimide fiber with high molecular weight and high crystallinity, but the choice of soluble monomer is limited and the use of toxic solvent severely restricts the development and large-scale application of the polyimide fiber; chinese patent ZL 02112048.X, US 4,370,290 and US 5,378,420 all disclose a one-step process for preparing polyimide fibers. 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 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, integrated continuous spinning and the like; chinese patent CN101338462B, CN112695402A, CN105297166B, CN105671680B, CN105237547B discloses a two-step process for preparing polyimide fibers.
Polyimide fibers are widely used in various high-tech fields as high-performance organic fibers. Along with the progress of science and technology, the service environment of the material is more severe, higher requirements are put forward on the performance of polyimide, and polyimide fibers are found in the application process of a high-orbit spacecraft, and the high-energy ultraviolet and space ray irradiation environment can accelerate the degradation and aging of the polyimide fibers, so that the performance and the service life of the fibers are seriously influenced, and the polyimide fibers are required to have more excellent irradiation resistance. Radiation resistant polyimide fibers have little research and limited alternatives to monomers and methods.
Disclosure of Invention
The technical problem solved by the application is to provide a preparation method of polyimide fiber, which has higher mechanical property, use temperature and 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 obtaining a polyamic acid spinning solution after polymerization reaction;
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 the formula (I1), the formula (I2) and the formula (I3);
the aromatic diamine is selected from one or more of a formula (II 1), a formula (II 2), a formula (II 3), a formula (II 4), a formula (II 5), a formula (II 6) and a 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 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 to 40 weight percent, the temperature of the polymerization reaction is-10 to 50 ℃ and the time is 5 to 72 hours.
Preferably, the spinning is dry-jet wet spinning or wet spinning;
the dry-jet wet spinning specifically comprises the following steps: sequentially filtering and vacuum defoamating the polyamic acid spinning solution, extruding the polyamic acid spinning solution through a metering pump through a spinneret orifice, and sequentially performing coagulating bath forming, water washing and drying after the polyamic acid spinning solution passes through an air layer to obtain polyamic acid fibers;
the wet spinning specifically comprises the following steps: and sequentially filtering and vacuum defoamating the polyamic acid spinning solution, extruding the polyamic acid spinning solution through a metering pump through a spinneret orifice, and finally sequentially performing coagulating bath forming, water washing and drying to obtain the polyamic acid fiber.
Preferably, in the dry-jet wet spinning process, the coagulating bath is a mixture of water and one of methanol, ethanol, glycol, butanol, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, 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 orifices is 20-1000, the spray 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, glycol, butanol, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, the aperture of the spinneret orifice is phi 0.04-phi 0.15mm, the number of the orifices is 30-12000, the spinneret 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 gradient heating atmosphere is air, nitrogen or argon.
Preferably, the imidization further comprises:
the imidized as-spun fibers are subjected to hot drawing.
Preferably, the temperature of the hot drawing is 300-600 ℃, the drawing multiplying power is 1.0-5.0, and the atmosphere is inert atmosphere.
The application provides a preparation method of polyimide fiber, which is characterized in that specific diamine and dianhydride monomers are polymerized to prepare polyamic acid spinning solution, the polyamic acid fiber is prepared after spinning, and then the polyamic acid fiber is dried and thermally imidized to obtain the polyimide fiber. According to the application, the structure of xanthone and acridone is introduced into a polyimide molecular chain, so that the mechanical property, the use temperature and the irradiation resistance of polyimide fibers are improved. The experimental results show that: the breaking strength of the polyimide fiber prepared by the application is 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 application;
FIG. 2 is a DMA curve of the polyimide fiber prepared in example 1 of the present application;
FIG. 3 is a TGA curve of polyimide fibers prepared in example 1 of the present application.
Detailed Description
For a further understanding of the present application, preferred embodiments of the application are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the application, and are not limiting of the claims of the application.
In view of the radiation resistance requirement of polyimide fibers in the prior art, the application introduces the structure of xanthone and acridone into a polyimide main chain, prepares novel polyimide fibers by a two-step method, improves the mechanical properties, the use temperature and the radiation resistance of the fibers, and is more suitable for being applied to the high-tech fields of aviation, nuclear power and the like. Specifically, the application 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 obtaining a polyamic acid spinning solution after polymerization reaction;
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 the formula (I1), the formula (I2) and the formula (I3);
the aromatic diamine is selected from one or more of a formula (II 1), a formula (II 2), a formula (II 3), a formula (II 4), a formula (II 5), a formula (II 6) and a 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 irradiation-resistant polyimide fiber provided by the application comprises four steps: preparing a polyamic acid spinning solution, preparing a polyamic acid fiber, imidizing the polyamic acid fiber and thermally drawing the polyimide fiber; in the steps, specific dianhydride and diamine monomers are introduced, and the xanthone and acridone structures are introduced into polyimide molecular chains, so that the mechanical properties, the use temperature and the irradiation resistance of the polyimide fiber are improved.
Specifically, in the preparation process, the application firstly prepares the polyamic acid spinning solution, which is obtained by mixing aromatic dianhydride and aromatic diamine in a solvent and polymerizing; the aromatic dianhydride is specifically selected from the following structures in this process, and the aromatic diamine is specifically selected from the following structures:
in specific embodiments, the aromatic dianhydride is selected from one or both of biphenyl tetracarboxylic dianhydride and pyromellitic dianhydride, and the aromatic diamine is specifically selected from the following combinations: p-and m-xanthone diamines, 4' -diaminodiphenyl ether and m-xanthone diamines, 2- (4-aminophenyl) -5-aminobenzimidazole and p-xanthone diamines, p-and acridone diamines. 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 to 40 weight percent, the temperature of the polymerization reaction is-10 to 50 ℃ and the time is 5 to 72 hours; more specifically, the polymerization reaction temperature is 0-20 ℃, and the polymerization reaction time is 12-24 hours.
The polyamic acid spinning solution is spun to obtain polyamic acid fiber; in this process, the spinning is performed according to a method well known to those skilled in the art, and specifically, dry spray wet spinning or wet spinning may be used; more specifically, the dry-jet wet spinning is: sequentially filtering and vacuum defoamating the polyamic acid spinning solution, extruding the polyamic acid spinning solution through a metering pump through a spinneret orifice, and sequentially performing coagulating bath forming, water washing and drying after the polyamic acid spinning solution passes through an air layer to obtain polyamic acid fibers;
the wet spinning specifically comprises the following steps: and sequentially filtering and vacuum defoamating the polyamic acid spinning solution, extruding the polyamic acid spinning solution through a metering pump through a spinneret orifice, and finally sequentially performing coagulating bath forming, water washing and drying to obtain the polyamic acid fiber.
In the dry-jet wet spinning process, the coagulating bath is a mixture of water and one of methanol, ethanol, glycol, butanol, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, 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 orifices is 50-400, the spray ratio is 1.0-7.0 times, and the speed is 5-100 m/min; specifically, the height of the air layer is 10-30 mm. The aperture of the spinneret orifice is phi 0.10-phi 0.15mm, the number of the orifices is 20-1000, the spinneret 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, glycol, butanol, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, the aperture of the spinneret orifice is phi 0.04-phi 0.15mm, the number of the orifices is 30-12000, the spinneret ratio is 1.0-5.0 times, and the speed is 5-100 m/min; specifically, the aperture of the spinneret orifice is phi 0.08-phi 0.12mm, the number of the orifices is 100-10000, the spinneret ratio is 1.5-4.0 times, and the speed is 20-60 m/min.
The polyamide acid fiber obtained by the method is imidized to obtain polyimide fiber; in the imidization process, a gradient heating mode is adopted, the temperature of the gradient heating is 50-500 ℃, the heating rate is 1-30 ℃/min, and the gradient heating atmosphere is air, nitrogen or argon; more specifically, the imidization temperature is 50-400 ℃ and the heating rate is 5-20 ℃/min.
Finally, the obtained nascent fiber is subjected to hot drawing, so that the polyimide fiber has good mechanical properties. 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 temperature of the hot drawing is 450-580 ℃, the drawing multiplying power is 1.2-2.0, and the atmosphere is nitrogen or argon.
In order to further understand the present application, the following examples are provided to illustrate the preparation method of the irradiation-resistant polyimide fiber according to the present application in detail, and the scope of the present application is not limited by the following examples.
And (3) testing the mechanical properties of the fibers by adopting a Textechno FAVIMAT single fiber tensile strength tester, wherein the tensile speed is 5mm/min, the initial modulus is measured to obtain the modulus of the strain of the stress-strain curve in the interval of 0.2% -0.4%, at least 10 samples are tested for each group of fibers, and the arithmetic average value is obtained.
Example 1
294.22g (1.0 mol) of biphenyl tetracarboxylic dianhydride, 97.33g (0.9 mol) of p-phenylenediamine, 22.62g (0.1 mol) of meta-xanthone diamine, 2347g of N, N-dimethylacetamide (DMAc) and a three-neck round bottom flask which is provided with mechanical stirring and nitrogen protection are added, and the mixture is reacted for 24 hours at the temperature of 0 ℃ to obtain a light yellow polyamic acid solution, and the light yellow polyamic acid solution is directly used as spinning slurry after being filtered;
spinning and forming the polyamide acid slurry by adopting a dry-jet wet spinning technology route, accurately metering the normal-temperature spinning slurry by using a metering pump, extruding the obtained product through a spinneret orifice, and then entering 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 0.14mm, the spray ratio is 4 times, the spinning speed is 50m/min, and the air layer height is 10mm; washing the nascent fiber with water, and drying the nascent fiber through 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 for 1.5 times at 500 ℃ in a nitrogen environment to obtain polyimide finished fiber.
According to the method of the technical scheme, the polyimide fiber prepared in the embodiment 1 of the application is tested for mechanical properties, 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 (1.0 mol) of pyromellitic dianhydride, 140.17g (0.7 mol) of 4,4' -diaminodiphenyl ether, 67.87g (0.3 mol) of meta-xanthone diamine, 2850g of N, N-dimethylacetamide (DMAc), and reacting at 10 ℃ for 12 hours to obtain a pale yellow polyamic acid solution, and filtering the pale yellow polyamic acid solution to be directly used as spinning slurry;
spinning and forming the polyamide acid slurry by adopting a dry-jet wet spinning technology route, accurately metering the normal-temperature spinning slurry by using a metering pump, extruding the metering pump from a spinneret orifice, and then feeding the metering pump into a coagulating bath of N, N-dimethylacetamide and water (1:3 volume ratio) through an air layer, wherein a 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 air layer height is 10mm; washing the nascent fiber with water, and drying the nascent fiber through 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 for 1.75 times at 500 ℃ in a nitrogen environment to obtain polyimide finished fiber.
According to the method of the technical scheme, the polyimide fiber prepared in the embodiment 2 of the application is tested for mechanical properties, 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
To a three-necked round bottom flask equipped with mechanical stirring and nitrogen protection was added 294.22g (1.0 mol) of biphenyl tetracarboxylic dianhydride, 112.13g (0.5 mol) of 2- (4-aminophenyl) -5-aminobenzimidazole, 113.12g (0.5 mol) of p-xanthone diamine, 3815g of N, N-Dimethylformamide (DMF), and the mixture was reacted at 0℃for 48 hours to obtain a pale yellow polyamic acid solution, which was directly used as a spinning dope after filtration;
spinning and forming the polyamide acid slurry by adopting a dry-jet wet spinning technology route, accurately metering the normal-temperature spinning slurry by using a metering pump, extruding the metering pump from a spinneret orifice, and then feeding the metering pump into a coagulating bath of N, N-dimethylformamide and water (1:2 volume ratio), wherein a 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 air layer height is 10mm; washing the nascent fiber with water, and drying the nascent fiber through 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 for 2.0 times at 530 ℃ in a nitrogen environment to obtain polyimide finished fiber.
According to the method of the technical scheme, the polyimide fiber prepared in the embodiment 3 of the application is tested for mechanical properties, 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 (1.0 mol) of biphenyl tetracarboxylic dianhydride, 75.70g (0.7 mol) of p-phenylenediamine, 67.87g (0.3 mol) of p-xanthone diamine, 2481g of N, N-Dimethylformamide (DMF) were added into a three-neck round bottom flask which is provided with mechanical stirring and nitrogen protection, and the mixture was reacted for 48 hours at 5 ℃ to obtain a light yellow polyamic acid solution, and the light yellow polyamic acid solution was directly used as spinning slurry after being filtered;
spinning and forming the polyamide acid slurry by adopting a dry-jet wet spinning technology route, accurately metering the normal-temperature spinning slurry by using a metering pump, extruding the metering pump from a spinneret orifice, and then feeding the metering pump into a coagulating bath of N, N-dimethylformamide and water (1:4 volume ratio), wherein a 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 air layer height is 10mm; washing the nascent fiber with water, and drying the nascent fiber through a hot nitrogen channel to obtain polyamide acid fiber;
and treating the polyamide acid fiber in a gradient heating thermal imidization furnace in a nitrogen environment to obtain the polyimide fiber. The thermal imidization temperature is 50-400 ℃ and the heating speed is 20 ℃/min; the obtained polyimide fiber is drafted for 1.75 times at 550 ℃ in a nitrogen environment to obtain polyimide finished fiber.
According to the method of the technical scheme, the mechanical properties of the polyimide fiber prepared in the embodiment 4 of the application are tested, and the test results are 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 (0.5 mol) of diphenyl tetrahydride, 109.06g (0.5 mol) of pyromellitic dianhydride, 226.24g (1 mol) of p-xanthone diamine, 2734g of N-methylpyrrolidone (NMP) and reacting at-10 ℃ for 24 hours to obtain a pale yellow polyamic acid solution, and filtering the pale yellow polyamic acid solution to be directly used as spinning slurry;
spinning and forming the polyamide acid slurry by adopting a dry-jet wet spinning technology route, accurately metering the normal-temperature spinning slurry by using a metering pump, extruding the metering pump from a spinneret orifice, and then feeding the metering pump into a coagulating bath of N-methylpyrrolidone and water (1:5 volume ratio) through an air layer, wherein a 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 air layer height is 15mm; washing the nascent fiber with water, and drying the nascent fiber through 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 for 1.5 times at 500 ℃ in a nitrogen environment to obtain polyimide finished fiber.
According to the method of the technical scheme, the polyimide fiber prepared in the embodiment 5 of the application is tested for mechanical properties, 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
218.12g (1.0 mol) of pyromellitic dianhydride, 54.07g (0.5 mol) of p-phenylenediamine, 112.63g (0.5 mol) of acridone diamine, 2810g of N, N-dimethylacetamide (DMAc) and a three-necked round bottom flask which is provided with mechanical stirring and nitrogen protection are added, and the mixture is reacted for 24 hours at the temperature of minus 10 ℃ to obtain a light yellow polyamic acid solution which is directly used as spinning slurry after being filtered;
spinning and forming the polyamide acid slurry by adopting a dry-jet wet spinning technology route, accurately metering the normal-temperature spinning slurry by using a metering pump, extruding the metering pump from a spinneret orifice, and then feeding the metering pump into a coagulating bath of N, N-dimethylacetamide and water (1:3 volume ratio) through an air layer, wherein a 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 air layer height is 10mm; washing the nascent fiber with water, and drying the nascent fiber through 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 for 1.25 times at 500 ℃ in a nitrogen environment to obtain polyimide finished fiber.
According to the method of the technical scheme, the polyimide fiber prepared in the embodiment 6 of the application is tested for mechanical properties, 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
294.22g (1.0 mol) of biphenyl tetracarboxylic dianhydride, 75.70g (0.7 mol) of p-phenylenediamine, 67.58g (0.3 mol) of acridone diamine, 2480g of N, N-dimethylacetamide (DMAc) and 24 hours of reaction at 0 ℃ are added into a three-neck round bottom flask which is provided with mechanical stirring and nitrogen protection, and the mixture is directly used as spinning slurry after being filtered;
spinning and forming the polyamide acid slurry by adopting a dry-jet wet spinning technology route, accurately metering the normal-temperature spinning slurry by using a metering pump, extruding the metering pump from a spinneret orifice, and then feeding the metering pump into a coagulating bath of N, N-dimethylacetamide and water (1:2 volume ratio) through an air layer, wherein a 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 air layer height is 10mm; washing the nascent fiber with water, and drying the nascent fiber through 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; drawing the obtained polyimide fiber at 530 ℃ for 2.0 times in a nitrogen environment to obtain polyimide finished fiber;
according to the method of the technical scheme, the polyimide fiber prepared in the embodiment 7 of the application is tested for mechanical properties, 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
294.22g (1.0 mol) of biphenyl tetracarboxylic dianhydride, 64.88g (0.6 mol) of p-phenylenediamine, 90.49g (0.4 mol) of meta-xanthone diamine, 2761g of N, N-Dimethylformamide (DMF), and reacting at 10 ℃ for 48 hours to obtain a light yellow polyamic acid solution, and filtering the light yellow polyamic acid solution to be directly used as spinning slurry;
spinning and forming the polyamide acid slurry by adopting a wet spinning technology route, accurately metering the normal-temperature spinning slurry by using a metering pump, extruding the metering pump from a spinneret orifice, and then feeding the metering pump into a coagulating bath of N, N-dimethylformamide and water (1:5 volume ratio), wherein a spinneret plate is 400 holes, the aperture phi is 0.12mm, the spray ratio is 3.5 times, and the spinning speed is 60m/min; washing the nascent fiber with water, and drying the nascent fiber through a hot nitrogen channel to obtain polyamide acid fiber;
and treating the polyamide acid fiber in a gradient heating thermal imidization furnace in a nitrogen environment to obtain the polyimide fiber. The thermal imidization temperature is 50-400 ℃ and the heating speed is 10 ℃/min; the obtained polyimide fiber is drafted for 2.0 times at 510 ℃ in a nitrogen environment to obtain polyimide finished fiber.
According to the method of the technical scheme, the polyimide fiber prepared in the embodiment 8 of the application is tested for mechanical properties, 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
294.22g (1.0 mol) of biphenyl tetracarboxylic dianhydride, 108.14g (1.0 mol) of p-phenylenediamine, and 2280g of N, N-dimethylacetamide (DMAc) were added into a three-necked round bottom flask equipped with mechanical stirring and nitrogen protection, and reacted at 0 ℃ for 24 hours to obtain a pale yellow polyamic acid solution, which was directly used as spinning slurry after filtration;
the polyimide fiber was prepared by using the above polyamic acid slurry in the same spinning, thermal imidization and hot drawing processes as in example 1.
According to the method of the technical scheme, the mechanical properties of the polyimide fiber prepared in the comparative example 1 are tested, and the test results are as follows: the breaking strength of the fiber is 1.0GPa, the modulus is 88.9GPa, and the breaking elongation is 1.7%.
Comparative example 2
218.12g (1.0 mol) of pyromellitic dianhydride, 200.24g (1.0 mol) of 4,4' -diaminodiphenyl ether and 2030g of N, N-dimethylacetamide (DMAc) were charged into a three-necked round bottom flask equipped with mechanical stirring and nitrogen protection, reacted at 10℃for 12 hours to obtain a pale yellow polyamic acid solution, which was directly used as spinning dope after filtration;
the polyimide fiber was prepared by using the above polyamic acid slurry in the same spinning, thermal imidization and hot drawing processes as in example 2.
According to the method of the technical scheme, the mechanical properties of the polyimide fiber prepared in the comparative example 2 are tested, and the test results show that the fiber breaking strength is 0.7GPa, the modulus is 9.6GPa and the breaking elongation is 8.2%.
Comparative example 3
To a three-necked round bottom flask equipped with mechanical stirring and nitrogen protection was added 294.22g (1.0 mol) of biphenyl tetracarboxylic dianhydride, 224.26g (1.0 mol) of 2- (4-aminophenyl) -5-aminobenzimidazole, 2938g of N, N-Dimethylformamide (DMF) and reacted at 0℃for 48 hours to obtain a pale yellow polyamic acid solution which was directly used as spinning dope after filtration;
the polyimide fiber was prepared by using the above polyamic acid slurry in the same spinning, thermal imidization and hot drawing processes as in example 3.
According to the method of the technical scheme, the mechanical properties of the polyimide fiber prepared in the comparative example 3 are tested, and the test results show that the fiber breaking strength is 1.7GPa, the modulus is 52.8GPa, and the breaking elongation is 3.1%.
The polyimide fibers obtained in examples 1 to 8 and comparative examples 1 to 3 were subjected to ultraviolet ray irradiation test, and the results are shown in Table 1, and Table 1 shows the results of the fiber breaking strength test before and after ultraviolet ray irradiation, the ultraviolet ray irradiation strength being 10.43w/m 2 The wavelength range is 280-315 nm.
TABLE 1 results of polyimide fiber breaking strength test before and after UV irradiation
Fig. 1 is an FT-IR spectrum of the polyimide fiber prepared in example 1, fig. 2 is a DMA curve of the polyimide fiber prepared in example 1, and fig. 3 is a TGA curve of the polyimide fiber prepared in example 1. As can be seen in FIG. 1, 1772, 1701, 1352cm -1 The existence of obvious characteristic peaks respectively belonging to an antisymmetric stretching vibration peak, a symmetrical stretching vibration peak and a C-N stretching vibration peak of the imine ring carbonyl group shows that polyimide fibers are successfully synthesized. As can be seen in FIG. 2, the polyimide fiber prepared in example 1 has a glass transition temperature of 322 ℃. As can be seen in FIG. 3, the prepared polyimide fibers have 5wt% thermal decomposition temperatures of 609℃and 575℃under nitrogen and air atmosphere, respectively.
The above description of the embodiments is only for aiding in the understanding of the method of the present application and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the application can be made without departing from the principles of the application and these modifications and adaptations are intended to be within the scope of the application as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. 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 application. Thus, the present application 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 (7)
1. A preparation method of radiation-resistant polyimide fibers comprises the following steps:
a) Mixing aromatic dianhydride and aromatic diamine in a solvent, and obtaining a polyamic acid spinning solution after polymerization reaction;
b) Spinning the polyamic acid spinning solution to obtain polyamic acid fiber;
c) Imidizing the polyamide acid fiber, and thermally drawing the imidized nascent fiber to obtain a polyimide fiber;
the aromatic dianhydride is selected from the formula (I1) or the formula (I2);
the aromatic diamine is selected from 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 acridone diamine;
（Ⅰ1）；/> （Ⅰ2）。
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 preparation method according to claim 1, wherein the solid content of the polyamic acid in the polyamic acid spinning solution is 5-40 wt%, the polymerization reaction temperature is-10-50 ℃ and the polymerization reaction time is 5-72 h.
4. The method according to claim 1, wherein the spinning is dry jet wet spinning or wet spinning;
the dry-jet wet spinning specifically comprises the following steps: sequentially filtering and vacuum defoamating the polyamic acid spinning solution, extruding the polyamic acid spinning solution through a metering pump through a spinneret orifice, and sequentially performing coagulating bath forming, water washing and drying after the polyamic acid spinning solution passes through an air layer to obtain polyamic acid fibers;
the wet spinning specifically comprises the following steps: and sequentially filtering and vacuum defoamating the polyamic acid spinning solution, extruding the polyamic acid spinning solution through a metering pump through a spinneret orifice, and finally sequentially performing coagulating bath forming, water 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 coagulation bath is a mixture of water and one of methanol, ethanol, glycol, butanol, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, 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 holes is 20-1000 holes, the spray 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, glycol, butanol, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, the aperture of the spinneret orifice is phi 0.04-phi 0.15mm, the number of the orifices is 30-12000, the spinneret 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 gradient heating temperature of 50 to 500 ℃, the heating rate is 1 to 30 ℃/min, and the gradient heating atmosphere is air, nitrogen or argon.
7. The method according to claim 1, wherein the temperature of the thermal draft is 300 to 600 ℃, the draft ratio is 1.0 to 5.0, and the atmosphere is an inert atmosphere.
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