CN115467051A - Carbon fiber and preparation method thereof - Google Patents
Carbon fiber and preparation method thereof Download PDFInfo
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- CN115467051A CN115467051A CN202211129202.7A CN202211129202A CN115467051A CN 115467051 A CN115467051 A CN 115467051A CN 202211129202 A CN202211129202 A CN 202211129202A CN 115467051 A CN115467051 A CN 115467051A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 42
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 107
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 101
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 101
- 238000002156 mixing Methods 0.000 claims abstract description 51
- 230000003647 oxidation Effects 0.000 claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 238000009987 spinning Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000004642 Polyimide Substances 0.000 claims abstract description 25
- 229920001721 polyimide Polymers 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229920005575 poly(amic acid) Polymers 0.000 claims description 68
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 47
- 239000000835 fiber Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000725 suspension Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 230000000087 stabilizing effect Effects 0.000 claims description 14
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 12
- 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 description 10
- 238000010000 carbonizing Methods 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 10
- 230000001112 coagulating effect Effects 0.000 claims description 9
- 239000002048 multi walled nanotube Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 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 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 2
- VKZZGCYGUAPPFC-UHFFFAOYSA-N 6-amino-2-(4-aminophenyl)-1h-quinazolin-4-one Chemical compound C1=CC(N)=CC=C1C1=NC(O)=C(C=C(N)C=C2)C2=N1 VKZZGCYGUAPPFC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 claims description 2
- 125000006159 dianhydride group Chemical group 0.000 claims description 2
- 239000002079 double walled nanotube Substances 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- 230000033444 hydroxylation Effects 0.000 claims description 2
- 238000005805 hydroxylation reaction Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 claims description 2
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006557 surface reaction Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 90
- 239000011550 stock solution Substances 0.000 abstract description 19
- 238000002166 wet spinning Methods 0.000 abstract description 7
- 238000003763 carbonization Methods 0.000 abstract description 5
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 238000001891 gel spinning Methods 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 hexafluoroisopropylidene Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of carbon nano tube reinforced polyimide/polyacrylonitrile blended carbon fiber, which comprises the steps of uniformly dispersing carbon nano tubes in a solvent by adopting a solution blending method, uniformly dispersing the carbon nano tubes in a polyamide acid and polyacrylonitrile blend which is used as a spinning solution by solution blending, and preparing a spinning stock solution in which the carbon nano tubes are dispersed; the carbon nanotube-reinforced polyimide and polyacrylonitrile blended carbon fiber is prepared by wet or dry-wet spinning processes, and is excellent in tensile and heat-conducting properties through heat treatment, pre-oxidation and carbonization processes.
Description
Technical Field
The invention relates to the technical field of carbon fibers, in particular to carbon nanotube reinforced polyimide and polyacrylonitrile blended carbon fibers and a preparation method thereof.
Background
In recent years, with the industrialization and low cost of various dianhydride and diamine monomers for synthesizing polyimide and the progress of polyimide synthesis and processing technology, the research and product development process of polyimide is greatly accelerated, and the application field is widened continuously. The aromatic heterocyclic framework structure and high carbon content of the polyimide make the polyimide have excellent graphitization property, and a carbon material with high graphitization, good conductivity and high magnetoresistance can be obtained. Polyimide fibers have the advantage of a highly oriented structure, and therefore, are considered to be excellent raw materials for preparing carbon fiber materials.
The carbon fiber formed by blending and pre-oxidizing the polyimide and the polyacrylonitrile has the characteristics of PI fiber and PAN fiber, and the polyimide has the characteristics of excellent heat resistance, good flame resistance, limited Oxygen Index (LOI) of 35-75% generally, low smoke generation rate and self-extinguishing material, so the carbon fiber has heat resistance compared with pure PAN-based carbon fiber.
The prior art discloses a method for reinforcing carbon fibers by carbon nanotubes, so that physical and mechanical properties are improved, and electrical and heat resistance and the like are improved, but most of the existing carbon fibers are acrylonitrile-based carbon fibers, and carbon nanotube reinforcement is not performed on carbon fibers formed by blending and pre-oxidizing polyimide and polyacrylonitrile.
Disclosure of Invention
The invention aims to provide a carbon nanotube reinforced polyimide and polyacrylonitrile blended carbon fiber, which improves the mechanical property and the heat conductivity of the existing polyimide and polyacrylonitrile blended carbon fiber. The principle of the invention is that a solution blending method is adopted to uniformly disperse carbon nano tubes in a solvent, and then the solution is uniformly dispersed in a polyamide acid and polyacrylonitrile blend which is used as a spinning solution through blending to prepare a spinning solution with dispersed carbon nano tubes; the carbon nanotube-reinforced polyimide and polyacrylonitrile blended carbon fiber is prepared by wet or dry-wet spinning processes and by heat treatment, pre-oxidation and carbonization processes.
Another object of the present invention is to provide a method for preparing carbon nanotube reinforced polyimide and polyacrylonitrile blended carbon fiber.
The preparation method of the carbon nano tube reinforced polyimide/polyacrylonitrile blended carbon fiber comprises the following steps:
a: dispersing carbon nano tubes into a solvent by ultrasonic to obtain a carbon nano tube suspension;
b: adding polyacrylonitrile powder into a solvent, swelling for 3-5 hours at 0-15 ℃, slowly heating to 60-80 ℃ in a water bath, continuously stirring for 1-3 hours, and cooling to obtain a polyacrylonitrile solution;
c: preparing a polyamic acid (PAA) solution by using diamine and dianhydride solution polymerization reaction;
d: in the protection of inert gas or air, mechanically stirring the carbon nanotube suspension obtained in the step A and the step C and the polyamic acid solution at room temperature, and mixing for 3-5 hours; stirring and adding the polyacrylonitrile solution obtained in the step B within 1-3 hours, mechanically stirring at room temperature after the material is added, continuously mixing for 2-4 hours, and finally uniformly mixing the polyacrylonitrile solution, the polyacrylonitrile solution and the polyacrylonitrile solution in the solution to obtain blended spinning solution; wherein, the carbon nano tube: PAN: PAA is mixed according to the following weight parts of 1-5;
e: defoaming the blended spinning solution prepared in the step D, and then spinning by a wet method or a dry wet method to prepare the CNT/PAA/PAN blended nascent fiber, wherein the spinning temperature is 30-50 ℃, the pore diameter of a spinneret orifice is 0.05-1 mm, the temperature of a coagulating bath is 25-30 ℃, the drawing speed is 5-20 m/min, and the drawing multiple is 5-15 times;
f: the primary fiber prepared in the E step is subjected to heat treatment to prepare CNT/PAA/PAN blending protofilament, wherein the heat treatment uses a layer type heat stabilizing furnace with 4 zones, and the temperature of each zone is as follows: the first zone is 60-90 ℃, the second zone is 70-100 ℃, the third zone is 80-120 ℃, the fourth zone is 110-160 ℃ to obtain the CNT/PAA/PAN blended protofilament, the temperature of the 4 zones is sequentially increased, the oxidation time is 0.5-1 hour at each temperature, and the atmosphere is air;
g: and (3) carrying out layer type pre-oxidation treatment on the protofilament prepared in the step F to obtain CNT/PAA/PAN blending pre-oxidation fibers, wherein the pre-oxidation treatment is 4 zones by using a layer type thermal stabilizing furnace, and the temperature of each zone is as follows: the temperature of the first zone is 180-210 ℃, the temperature of the second zone is 200-240 ℃, the temperature of the third zone is 230-270 ℃, the temperature of the fourth zone is 260-300 ℃, the temperature of the 4 zones is increased in sequence, the oxidation time at each temperature is 0.5-1 hour, and the atmosphere is air;
and H, carbonizing the CNT/PAA/PAN blended pre-oxidized fiber prepared in the step G to obtain the carbon nanotube reinforced PAA/PAN blended carbon fiber, wherein the carbonization treatment is carried out by a low-carbon furnace at 500-700 ℃ for 20-60 minutes, then the carbon nanotube reinforced PAA/PAN blended carbon fiber is transferred to a high-carbon furnace at 900-1100 ℃ for 10-30 minutes, and high-purity nitrogen is used for protection.
The reaction solvent adopted in the steps A, B and C is any one or a mixture of several of dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc). Dimethyl sulfoxide (DMSO) is preferred, and CNT, PAA and PAN are more uniformly dispersed in the solvent.
The carbon nano-tube (CNT) in the step A is one, two or three of multi-wall carbon nano-tube, single-wall carbon nano-tube and double-wall carbon nano-tube, the diameter of the carbon nano-tube is 1-30 nanometers, and the length of the carbon nano-tube is 0.1-2 micrometers. The surface functionalized carbon nano-tubes can be directly used, and more preferably, the carbon nano-tubes with functionalized surfaces such as amination, sulfonation or hydroxylation are adopted, and after the functionalized groups are carried on the surfaces of the carbon nano-tubes, the surface polarity is greatly enhanced, so that the carbon nano-tubes are more favorably dispersed in a mixed solution.
The polyamic acid solution in step C may be prepared by a polycondensation reaction of one diamine and one dianhydride, or by a copolycondensation reaction of any one or more diamines and any one or more dianhydrides, or by a blending of any several mixed polycondensation type or copolycondensation type polyamic acids, wherein the diamine monomer is a general diamine monomer capable of preparing polyimide, and preferably includes 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (p-PDA), 4' -diaminodiphenylmethane (MDA), 2- (4-aminophenyl) -5-aminobenzimidazole (BIA), 2- (4-aminophenyl) -6-amino-4 (3H) -quinazolinone (AAQ); the dianhydride monomer is a general dianhydride monomer that can prepare polyimide, and preferably includes 3,3', 4' -benzophenone tetracarboxylic dianhydride (BPDA), 3',4,4' -biphenyltetracarboxylic dianhydride (ODPA), pyromellitic dianhydride (PMDA), 3', 4' -benzophenonetetracarboxylic dianhydride (BTDA), 4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA).
In the step E, the coagulating bath is water or a mixture of a solvent and water, and the volume ratio of the solvent to the water is 1: 3-3: 1.
The carbon nanotube reinforced polyimide/polyacrylonitrile blended carbon fiber further improves the mechanical property and the heat conduction property of the carbon fiber, has simple process, can improve the dispersibility and the interface bonding force of the carbon nanotube in a blended polymer matrix, and has smooth surface, dense section, no holes and excellent mechanical property. The tensile strength can be more than 1.8GPa, the axial thermal conductivity of the carbon fiber is more than 350W/(m.K), and the carbon fiber has better heat resistance and flame retardance.
In addition, the carbon nanotube-reinforced polyimide and polyacrylonitrile blended carbon fiber according to the specific ratio of the invention is better in tensile strength and heat conductivity than the carbon nanotube-free carbon fiber blended carbon fiber in which the content ratio of the carbon nanotube-reinforced polyimide and the polyacrylonitrile is not in the range, and in addition, the carbon nanotube suspension is mixed with the polyamic acid solution in the mixing step and then mixed with the polyacrylonitrile solution, so that the carbon nanotube has better dispersion effect on the carbon nanotube, thereby being beneficial to the tensile and heat conductivity of the final carbon fiber, and the performance of the final carbon fiber is deteriorated without additionally adding a dispersion aid aiming at the carbon nanotube. It is presumed that the carbon nanotubes have a polarity close to that of the polyamic acid solution, which is favorable for the dispersion of the carbon nanotubes in the polyamic acid solution, and do not affect the imidization reaction of the carbon nanotubes, and are mixed with the polyacrylonitrile solution, so that the carbon nanotubes have better interface performance.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be noted that: the following examples are intended to illustrate the invention and are not intended to limit the technical solutions described in the invention; thus, although the present invention has been described in detail with reference to the following examples, it will be understood by those skilled in the art that the present invention may be modified and equivalents may be substituted; all such modifications and variations that do not depart from the spirit and scope of the invention are intended to be included within the scope of the appended claims.
Example 1:
a: preparing a carbon nano tube suspension: dispersing 2g of aminated multi-walled carbon nanotubes into DMSO (dimethyl sulfoxide) by ultrasonic to obtain a carbon nanotube suspension;
b, preparing polyacrylonitrile stock solution: adding 60g of polyacrylonitrile powder into DMSO, swelling for 3 hours at 0 ℃, slowly heating to 60 ℃ in a water bath, continuously stirring for 2 hours, and cooling to obtain a polyacrylonitrile solution;
and C, synthesizing and preparing polyamic acid stock solution: 0.21mol of BPDA, 0.1mol of ODA and 0.1mol of p-PDA were dissolved in DMSO, and mechanically stirred at 5 ℃ for 2 hours to prepare a polyamic acid solution of BPDA/ODA/p-PDA.
D, mixing stock solution: c, mechanically stirring the carbon nano tube suspension obtained in the step A and the polyamic acid solution obtained in the step C at room temperature, and mixing for 3 hours; then adding the polyacrylonitrile solution obtained in the step B, mechanically stirring at room temperature, continuously mixing for 3 hours, and finally uniformly mixing the polyacrylonitrile solution, the polyacrylonitrile solution and the solution in the solution to obtain blended spinning solution;
e: spinning and stretching: and D, defoaming the blended spinning solution prepared in the step D, and then performing wet spinning, wherein the spinning temperature is 40 ℃, the pore diameter of a spinneret orifice is 0.08mm, and the volume ratio of water to water is 1: DMSO is used as a coagulating bath, the temperature is controlled to be 25 ℃, the drawing speed is 10m/min, and the drawing multiple is 10 times, so that the CNT/PAA/PAN blending nascent fiber is obtained;
f: heat treatment of the blended precursor: and E, performing heat treatment on the blended nascent fiber prepared in the step E to prepare CNT/PAA/PAN blended protofilament, wherein the heat treatment uses a layer type heat stabilizing furnace with 4 zones in an air atmosphere, and the temperature of each zone is as follows: the first zone is 75 ℃, the second zone is 90 ℃, the third zone is 100 ℃ and the fourth zone is 150 ℃ to obtain CNT/PAA/PAN blended protofilaments, and the oxidation time is 1 hour at each temperature;
g: pre-oxidation treatment: and (3) carrying out layer type pre-oxidation treatment on the protofilament prepared in the step (F), wherein the pre-oxidation treatment uses a layer type thermal stabilizing furnace with 4 zones and an air atmosphere, and the temperature of each zone is as follows: the oxidation time of the first zone is 200 ℃, the second zone is 220 ℃, the third zone is 250 ℃, the fourth zone is 280 ℃ and each temperature is 1 hour;
h, carbonization treatment: and (3) carbonizing the CNT/PAA/PAN blended pre-oxidized fiber prepared in the step G, treating the fiber at 600 ℃ for 40 minutes by a low-carbon furnace, and then treating the fiber at 1000 ℃ for 20 minutes by a high-purity nitrogen gas in the process.
Example 2:
a: preparing a carbon nano tube suspension: dispersing 4g of aminated multi-walled carbon nanotubes into DMSO (dimethylsulfoxide) by ultrasonic to obtain a carbon nanotube suspension;
b: preparing polyacrylonitrile stock solution: adding 80g of polyacrylonitrile powder into DMSO, swelling for 3 hours at 0 ℃, slowly heating to 70 ℃ in a water bath, continuously stirring for 2 hours, and cooling to obtain a polyacrylonitrile solution;
c: synthesizing and preparing a polyamic acid stock solution: 0.31mol of BPDA, 0.15mol of ODA and 0.15mol of p-PDA were dissolved in DMSO, and mechanically stirred at 5 ℃ for 2 hours to prepare a polyamic acid solution of BPDA/ODA/p-PDA.
D: mixing stock solutions: mechanically stirring the carbon nano tube suspension obtained in the step A and the polyamic acid solution obtained in the step C at room temperature, and mixing for 3 hours; adding the polyacrylonitrile solution obtained in the step B, mechanically stirring at room temperature, continuously mixing for 3 hours, and finally uniformly mixing the polyacrylonitrile solution, the polyacrylonitrile solution and the solution in the solution to obtain blended spinning solution;
e: spinning and stretching: and D, defoaming the blended spinning solution prepared in the step D, and then performing wet spinning, wherein the spinning temperature is 40 ℃, the pore diameter of a spinneret orifice is 0.08mm, and the volume ratio of water to water is 1: DMSO is used as a coagulating bath, the temperature is controlled to be 25 ℃, the drawing speed is 10m/min, and the drawing multiple is 12 times, so that the CNT/PAA/PAN blending nascent fiber is obtained;
f: and (3) heat treatment of the blended protofilament: and E, performing heat treatment on the blended nascent fiber prepared in the step E to prepare CNT/PAA/PAN blended protofilament, wherein the heat treatment uses a layer type heat stabilizing furnace with 4 zones in an air atmosphere, and the temperature of each zone is as follows: the first zone is 75 ℃, the second zone is 90 ℃, the third zone is 100 ℃ and the fourth zone is 150 ℃ to obtain CNT/PAA/PAN blended protofilaments, and the oxidation time is 1 hour at each temperature;
g: pre-oxidation treatment: and F, carrying out layer-type pre-oxidation treatment on the precursor prepared in the step F, wherein the pre-oxidation treatment uses a layer-type thermal stabilizing furnace with 4 zones in an air atmosphere, and the temperature of each zone is as follows: the oxidation time of the first zone is 200 ℃, the second zone is 220 ℃, the third zone is 250 ℃, the fourth zone is 280 ℃ and each temperature is 1 hour;
h, carbonization treatment: and C, carbonizing the CNT/PAA/PAN blended pre-oxidized fiber prepared in the step G, treating the fiber for 40 minutes at 600 ℃ through a low-carbon furnace, and then transferring the fiber to a high-carbon furnace for treating for 20 minutes at 1000 ℃, wherein high-purity nitrogen is used for protection in the process.
Example 3:
a: preparing a carbon nano tube suspension: dispersing 1.5g of aminated multi-wall carbon nanotubes into DMSO (dimethyl sulfoxide) by ultrasonic to obtain a carbon nanotube suspension;
b: preparing polyacrylonitrile stock solution: adding 45g of polyacrylonitrile powder into DMSO, swelling for 3 hours at 0 ℃, slowly heating to 60 ℃ in a water bath, continuously stirring for 2 hours, and cooling to obtain a polyacrylonitrile solution;
c: synthesizing and preparing a polyamic acid stock solution: 0.17mol of BPDA, 0.08mol of ODA and 0.08mol of p-PDA were dissolved in DMSO, and mechanically stirred at 5 ℃ for 2 hours to prepare a polyamic acid solution of BPDA/ODA/p-PDA.
D: mixing stock solution: mechanically stirring the carbon nano tube suspension obtained in the step A and the polyamic acid solution obtained in the step C at room temperature, and mixing for 3 hours; adding the polyacrylonitrile solution obtained in the step B, mechanically stirring at room temperature, continuously mixing for 3 hours, and finally uniformly mixing the polyacrylonitrile solution, the polyacrylonitrile solution and the solution in the solution to obtain blended spinning solution;
e: spinning and stretching: and D, defoaming the blended spinning solution prepared in the step D, and then performing wet spinning, wherein the spinning temperature is 35 ℃, the pore diameter of a spinneret orifice is 0.05mm, and the volume ratio of water to water is 1: DMSO is used as a coagulating bath, the temperature is controlled to be 25 ℃, the drawing speed is 10m/min, and the drawing multiple is 8 times, so that the CNT/PAA/PAN blended nascent fiber is obtained;
f: and (3) heat treatment of the blended protofilament: the blended nascent fiber prepared in the E step is subjected to heat treatment to prepare CNT/PAA/PAN blended protofilament, wherein the heat treatment uses a layer type heat stabilizing furnace with 4 zones of air atmosphere, and the temperature of each zone is as follows: the first zone is 75 ℃, the second zone is 90 ℃, the third zone is 100 ℃ and the fourth zone is 150 ℃ to obtain CNT/PAA/PAN blended protofilaments, and the oxidation time is 1 hour at each temperature;
g: pre-oxidation treatment: and F, carrying out layer-type pre-oxidation treatment on the precursor prepared in the step F, wherein the pre-oxidation treatment uses a layer-type thermal stabilizing furnace with 4 zones in an air atmosphere, and the temperature of each zone is as follows: the oxidation time of the first zone is 200 ℃, the second zone is 220 ℃, the third zone is 250 ℃, the fourth zone is 280 ℃ and each temperature is 1 hour;
h: carbonizing treatment: and (3) carbonizing the CNT/PAA/PAN blended pre-oxidized fiber prepared in the step G, treating the fiber at 600 ℃ for 40 minutes by a low-carbon furnace, and then treating the fiber at 1000 ℃ for 20 minutes by a high-purity nitrogen gas in the process.
Example 4:
a: preparing a carbon nano tube suspension: dispersing 2g of aminated multi-walled carbon nanotubes into DMSO (dimethyl sulfoxide) by ultrasonic to obtain a carbon nanotube suspension;
b: preparing polyacrylonitrile stock solution: adding 60g of polyacrylonitrile powder into DMSO, swelling for 3 hours at 0 ℃, slowly heating to 60 ℃ in a water bath, continuously stirring for 2 hours, and cooling to obtain a polyacrylonitrile solution;
c: synthesizing and preparing a polyamic acid stock solution: 0.21mol of BPDA, 0.1mol of ODA and 0.1mol of p-PDA were dissolved in DMSO, and mechanically stirred at 5 ℃ for 2 hours to prepare a polyamic acid solution of BPDA/ODA/p-PDA.
D: mixing stock solution: c, mechanically stirring the carbon nano tube suspension obtained in the step A and the polyamic acid solution obtained in the step C at room temperature, and mixing for 3 hours; adding the polyacrylonitrile solution obtained in the step B, mechanically stirring at room temperature, continuously mixing for 3 hours, and finally uniformly mixing the polyacrylonitrile solution, the polyacrylonitrile solution and the solution in the solution to obtain blended spinning solution;
e: spinning and stretching: defoaming the blended spinning solution prepared in the step D, and then carrying out wet spinning, wherein the spinning temperature is 40 ℃, the pore diameter of a spinneret orifice is 0.08mm, and the volume ratio of water is 1: DMSO is used as a coagulating bath, the temperature is controlled to be 25 ℃, the drawing speed is 10m/min, and the drawing multiple is 10 times, so that the CNT/PAA/PAN blended nascent fiber is obtained;
f: and (3) heat treatment of the blended protofilament: the blended nascent fiber prepared in the E step is subjected to heat treatment to prepare CNT/PAA/PAN blended protofilament, wherein the heat treatment uses a layer type heat stabilizing furnace with 4 zones of air atmosphere, and the temperature of each zone is as follows: the CNT/PAA/PAN blended protofilament is obtained at 65 ℃ in the first area, 80 ℃ in the second area, 85 ℃ in the third area and 120 ℃ in the fourth area, and the oxidation time is 0.6 hour at each temperature;
g: pre-oxidation treatment: and (3) carrying out layer type pre-oxidation treatment on the protofilament prepared in the step (F), wherein the pre-oxidation treatment uses a layer type thermal stabilizing furnace with 4 zones and an air atmosphere, and the temperature of each zone is as follows: the oxidation time of the first zone is 180 ℃, the second zone is 210 ℃, the third zone is 230 ℃, the fourth zone is 265 ℃, and the oxidation time is 0.6 hour at each temperature;
h: carbonizing treatment: and (3) carbonizing the CNT/PAA/PAN blended pre-oxidized fiber prepared in the step G, treating the fiber at 550 ℃ for 30 minutes by a low-carbon furnace, and then treating the fiber at 900 ℃ for 15 minutes by a high-purity nitrogen furnace in the process.
Example 5:
a: preparing a carbon nano tube suspension: dispersing 2g of aminated multi-walled carbon nanotubes into DMSO (dimethyl sulfoxide) by ultrasonic to obtain a carbon nanotube suspension;
b: preparing polyacrylonitrile stock solution: adding 60g of polyacrylonitrile powder into DMSO, swelling for 3 hours at 0 ℃, slowly heating to 60 ℃ in a water bath, continuously stirring for 2 hours, and cooling to obtain a polyacrylonitrile solution;
c: synthesizing and preparing a polyamic acid stock solution: 0.21mol of BPDA, 0.1mol of ODA and 0.1mol of p-PDA were dissolved in DMSO, and mechanically stirred at 5 ℃ for 2 hours to prepare a polyamic acid solution of BPDA/ODA/p-PDA.
D: mixing stock solution: mechanically stirring the carbon nano tube suspension obtained in the step A and the polyamic acid solution obtained in the step C at room temperature, and mixing for 3 hours; then adding the polyacrylonitrile solution obtained in the step B, mechanically stirring at room temperature, continuously mixing for 3 hours, and finally uniformly mixing the polyacrylonitrile solution, the polyacrylonitrile solution and the solution in the solution to obtain blended spinning solution;
e: spinning and stretching: and D, defoaming the blended spinning solution prepared in the step D, and then performing wet spinning, wherein the spinning temperature is 40 ℃, the pore diameter of a spinneret orifice is 0.08mm, and the volume ratio of water to water is 1: DMSO is used as a coagulating bath, the temperature is controlled to be 25 ℃, the drawing speed is 10m/min, and the drawing multiple is 10 times, so that the CNT/PAA/PAN blending nascent fiber is obtained;
f: and (3) heat treatment of the blended protofilament: the blended nascent fiber prepared in the E step is subjected to heat treatment to prepare CNT/PAA/PAN blended protofilament, wherein the heat treatment uses a layer type heat stabilizing furnace with 4 zones of air atmosphere, and the temperature of each zone is as follows: the first zone is 90 ℃, the second zone is 100 ℃, the third zone is 115 ℃ and the fourth zone is 160 ℃ to obtain CNT/PAA/PAN blended protofilaments, and the oxidation time is 1 hour at each temperature;
g: pre-oxidation treatment: and F, carrying out layer-type pre-oxidation treatment on the precursor prepared in the step F, wherein the pre-oxidation treatment uses a layer-type thermal stabilizing furnace with 4 zones in an air atmosphere, and the temperature of each zone is as follows: the oxidation time at each temperature of the first zone is 210 ℃, the second zone is 240 ℃, the third zone is 270 ℃, the fourth zone is 290 ℃ for 1 hour;
h: carbonizing treatment: and (3) carbonizing the CNT/PAA/PAN blended pre-oxidized fiber prepared in the step G, treating the fiber at 700 ℃ for 50 minutes by a low-carbon furnace, and then treating the fiber at 1100 ℃ for 30 minutes by a high-purity nitrogen furnace in the process.
Comparative example 1:
the difference from example 1 is that: 2g of aminated carbon nanotubes were not added, and the other steps and processes were the same.
Comparative example 2:
the difference from example 1 is that: the addition amount of the aminated multi-walled carbon nanotubes in the step A is 8g, and other steps and processes are the same.
Comparative example 3:
the difference from example 1 is that: the addition amount of the aminated multi-walled carbon nanotube in the step A is 1g, and other steps and processes are the same.
Comparative example 4:
the difference from example 1 is that:
d: mixing stock solutions: and C, simultaneously mixing the carbon nano tube suspension obtained in the step A, the polyacrylonitrile solution obtained in the step B and the polyamic acid solution obtained in the step C, mechanically stirring for 3 hours in the poem, and carrying out other steps and processes in the same way.
Comparative example 5:
the difference from example 1 is that:
d: mixing stock solution: mechanically stirring the carbon nano tube suspension obtained in the step A and the polyacrylonitrile solution obtained in the step B at room temperature, and mixing for 3 hours; then adding the polyamic acid solution obtained in the step C, mechanically stirring at room temperature, continuously mixing for 3 hours, and finally uniformly mixing the polyamic acid solution, the polyamic acid solution and the solution to obtain blended spinning solution; other steps and processes are the same.
Comparative example 6:
the difference from comparative example 5 is that:
d: mixing stock solutions: mechanically stirring the carbon nano tube suspension obtained in the step A, the polyacrylonitrile solution obtained in the step B and 0.1g of dispersant sodium dodecyl sulfate at room temperature, and mixing for 3 hours; then adding the polyamic acid solution obtained in the step C, mechanically stirring at room temperature, continuously mixing for 3 hours, and finally uniformly mixing the polyamic acid solution, the polyamic acid solution and the solution to obtain blended spinning solution; other steps and processes are the same.
Table 1 shows the tensile strength, thermal conductivity in the axial direction of the carbon fiber, and heat resistance (limiting oxygen index) of the carbon fibers prepared in examples 1 to 5 and comparative examples 1 to 6.
Table 1: relevant Performance test indexes of examples 1 to 5 and comparative examples 1 to 6
Therefore, the carbon nanotube reinforced polyimide and polyacrylonitrile blended carbon fiber with the specific ratio is better in tensile strength and heat conduction performance than the carbon nanotube not added, the content ratio of the three is out of the range, and the carbon nanotube suspension is mixed with the polyamic acid solution and then mixed with the polyacrylonitrile solution in the mixing step, so that the carbon nanotube has better dispersion effect, the tensile and heat conduction performance of the final carbon fiber is facilitated, and the influence of adding other dispersion auxiliaries on the performance is avoided. The tensile strength can be more than 1.8GPa, the axial thermal conductivity of the carbon fiber is more than 350W/(m.K), and the carbon fiber has better heat resistance and flame retardance.
Although the present invention has been described to a certain degree, it will be apparent that various modifications may be made without departing from the spirit and scope of the invention. It is to be understood that the invention is not limited to the described embodiments, but is to be accorded the scope consistent with the claims, including equivalents of each element described.
Claims (8)
1. A preparation method of carbon nano tube reinforced polyimide/polyacrylonitrile blended carbon fiber is characterized by comprising the following steps:
a: dispersing carbon nano tubes into a solvent by ultrasonic to obtain a carbon nano tube suspension;
b: adding polyacrylonitrile powder into a solvent, swelling for 3-5 hours at 0-15 ℃, slowly heating to 60-80 ℃ in a water bath, continuously stirring for 1-3 hours, and cooling to obtain a polyacrylonitrile solution;
c: preparing a polyamic acid solution by using diamine and dianhydride solution polymerization reaction;
d: in the presence of inert gas or air, mechanically stirring the carbon nano tube suspension obtained in the step A and the carbon nano tube suspension obtained in the step C and the polyamic acid solution at room temperature, and mixing for 3-5 hours; stirring and adding the polyacrylonitrile solution obtained in the step B within 1-3 hours, mechanically stirring at room temperature after the material is added, continuously mixing for 2-4 hours, and finally uniformly mixing the polyacrylonitrile solution, the polyacrylonitrile solution and the polyacrylonitrile solution in the solution to obtain blended spinning solution; wherein the carbon nanotube: PAN: PAA is mixed according to the following weight parts of 1-5;
e: defoaming the blended spinning solution prepared in the step D, and then spinning by a wet method or a dry wet method to prepare the carbon nano tube/polyamic acid/polyacrylonitrile blended nascent fiber, wherein the spinning temperature is 30-50 ℃, the pore diameter of a spinneret orifice is 0.05-1 mm, the temperature of a coagulating bath is 25-30 ℃, the drawing speed is 5-20 m/min, and the drawing multiple is 5-15 times;
f: and E, performing heat treatment on the nascent fiber prepared in the step E to prepare the carbon nano tube/polyamic acid/polyacrylonitrile blended protofilament, wherein the heat treatment uses a layer type heat stabilizing furnace with 4 zones, and the temperature of each zone is as follows: the first zone is 60-90 ℃, the second zone is 70-100 ℃, the third zone is 80-120 ℃ and the fourth zone is 110-160 ℃ to obtain carbon nano tube/polyamic acid/polyacrylonitrile blended protofilament, the temperature of the 4 zones is raised in sequence, the oxidation time at each temperature is 0.5-1 hour, and the atmosphere is air;
g: and D, performing layer-type pre-oxidation treatment on the precursor prepared in the step F to obtain carbon nano tube/polyamic acid/polyacrylonitrile blended pre-oxidized fiber, wherein the pre-oxidation treatment uses a layer-type thermal stabilizing furnace which comprises 4 zones, and the temperature of each zone is as follows: the temperature of the first zone is 180-210 ℃, the second zone is 200-240 ℃, the third zone is 230-270 ℃, the fourth zone is 260-300 ℃, the temperature of the 4 zones is increased in sequence, the oxidation time is 0.5-1 hour at each temperature, and the atmosphere is air;
h: and C, carbonizing the CNT/PAA/PAN blended pre-oxidized fiber prepared in the step G to obtain the carbon nanotube reinforced PAA/PAN blended carbon fiber, treating the carbon nanotube reinforced PAA/PAN blended carbon fiber at 500-700 ℃ for 20-60 minutes by a low-carbon furnace, then treating the carbon nanotube reinforced PAA/PAN blended carbon fiber at 900-1100 ℃ for 10-30 minutes by a high-carbon furnace, and protecting the carbon nanotube reinforced PAA/PAN blended carbon fiber by using high-purity nitrogen.
2. The preparation method according to claim 1, wherein the reaction solvent used in steps A, B and C is any one or more of dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
3. The method according to claim 2, wherein the reaction solvent used in steps A, B and C is dimethyl sulfoxide.
4. The method according to claim 1, wherein the carbon nanotubes in step a are one, two or three of multi-wall carbon nanotubes, single-wall carbon nanotubes and double-wall carbon nanotubes, and the carbon nanotubes have a diameter of 1 to 30 nm and a length of 0.1 to 2 μm.
5. The method according to claim 4, wherein the carbon nanotubes in step A are subjected to surface functionalization by amination, sulfonation or hydroxylation.
6. The method according to claim 1, wherein the polyamic acid solution in step C is prepared by polycondensation reaction of a diamine and a dianhydride, or copolycondensation reaction of any one or more diamines and any one or more dianhydrides, or blending any several mixed polycondensation type or copolycondensation type polyamic acids, wherein the diamine monomer is selected from the group consisting of one or more of 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (p-PDA), 4' -diaminodiphenylmethane (MDA), 2- (4-aminophenyl) -5-aminobenzimidazole (BIA), 2- (4-aminophenyl) -6-amino-4 (3H) -quinazolinone (AAQ); the dianhydride monomer is selected from one or more of 3,3', 4' -benzophenone tetracarboxylic dianhydride (BPDA), 3', 4' -biphenyl tetracarboxylic dianhydride (ODPA), pyromellitic dianhydride (PMDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA).
7. The method of claim 1, wherein the coagulating bath in step E is water or a mixture of solvent and water, and the volume ratio of solvent to water is 1: 3-3: 1.
8. The carbon nanotube-reinforced polyimide/polyacrylonitrile blended carbon fiber produced by the production method according to any one of claims 1 to 7.
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