CN108486691B - Pre-oxidation accelerator for polyacrylonitrile-based carbon fiber precursors and use method thereof - Google Patents
Pre-oxidation accelerator for polyacrylonitrile-based carbon fiber precursors and use method thereof Download PDFInfo
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- CN108486691B CN108486691B CN201810250722.0A CN201810250722A CN108486691B CN 108486691 B CN108486691 B CN 108486691B CN 201810250722 A CN201810250722 A CN 201810250722A CN 108486691 B CN108486691 B CN 108486691B
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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
- D01F9/225—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 from stabilised polyacrylonitriles
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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
- 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
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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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
Abstract
The invention relates to a polyacrylonitrile-based carbon fiber precursor preoxidation accelerant and a use method thereof, the accelerant is one or more of dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide and other peroxides with half-life period of 1-60 minutes at 200 ℃, and the polyacrylonitrile precursor preoxidation temperature is reduced by more than 10 ℃ and the preoxidation time is reduced by more than 16.7 percent by adding the accelerant into or soaking the accelerant in any one or more of the processes of preparation of polyacrylonitrile spinning solution, spinning of precursor and preoxidation treatment, so that the energy consumption in the process of preparing carbon fibers is effectively reduced, the production efficiency is improved, and the accelerant has the advantages of simple operation process, low cost, less investment, compatibility with the existing carbon fiber production equipment and the like.
Description
Technical Field
The invention relates to a polyacrylonitrile-based carbon fiber precursor preoxidation accelerant and a use method thereof, belonging to the field of carbon fiber preparation.
Background
The carbon fiber has the characteristics of high specific strength, high specific modulus, high temperature resistance, corrosion resistance, good electric and thermal conductivity and the like, is an important reinforcement of an advanced composite material, and is widely applied to the fields of aerospace, transportation, building energy, sports and leisure and the like. In the preparation, production and application processes of the carbon fiber, the mechanical property and the importance of the carbon fiber are accurately and timely represented. The preparation process of the polyacrylonitrile-based carbon fiber comprises basic process procedures of polymerization, spinning, pre-oxidation, carbonization and the like, wherein the pre-oxidation is a bridge for converting fibers from organic to inorganic and has important influence on the performance of the final carbon fiber. The pre-oxidation process is also the phase of the carbon fiber preparation process which takes the longest time and consumes the most energy. The pre-oxidation of the polyacrylonitrile protofilament generally refers to a process of carrying out long-time heat treatment at the temperature of 200-300 ℃ in an air atmosphere. Accelerating the pre-oxidation speed and reducing the pre-oxidation temperature have important significance for saving energy, reducing consumption, improving production efficiency and reducing production cost in carbon fiber production. Chinese patent 200910234656.9 discloses a method for dipping polyacrylonitrile protofilament in potassium permanganate aqueous solution to reduce pre-oxidation temperature and improve pre-oxidation degree, but potassium permanganate aqueous solution has corrosivity and produces adverse effect on related equipment, and potassium ions may be introduced into fiber to form defects and influence performance of carbon fiber; chinese patent 201010285139.7 discloses that polyacrylonitrile precursor is impregnated with an aqueous ozone solution to increase the pre-oxidation rate and lower the pre-oxidation temperature, but ozone itself is a gas, is easily decomposed into oxygen, hardly forms a stable solution in water, and itself has an adverse effect on the environment.
Disclosure of Invention
The invention aims to provide a preoxidation accelerant for polyacrylonitrile-based carbon fiber precursors and a using method thereof. According to the invention, the peroxide with a higher decomposition temperature is selected and decomposed at the preoxidation temperature of the polyacrylonitrile precursor to form the free radical, so that the cyano group of the polyacrylonitrile is initiated and accelerated to form a cyclization structure, the energy consumption in the carbon fiber preparation process is effectively reduced, and the production efficiency is improved.
The invention provides a preoxidation accelerant of polyacrylonitrile-based carbon fiber precursor, which is peroxide with half-life of 1-60 minutes at 200 ℃.
The peroxide is one or more of dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide and di-tert-butyl peroxide.
The invention also provides a use method of the preoxidation accelerant for the polyacrylonitrile-based carbon fiber precursor, and the preoxidation accelerant is used in any one or any several processes of preparation of polyacrylonitrile spinning solution, precursor spinning and preoxidation treatment.
The polyacrylonitrile spinning solution is used in the preparation process, namely, a pre-oxidation accelerant is added into an acrylonitrile polymerization formula, wherein the mass of the pre-oxidation accelerant accounts for 0.1-5% of that of an acrylonitrile monomer or polyacrylonitrile.
The spinning of the protofilament refers to that the fiber stays in an accelerator solution with the mass fraction of 0.1-10% for 0.1-5 seconds after solidification, traction, water washing, oiling and heat setting.
The pre-oxidation treatment is used by allowing polyacrylonitrile protofilament to stay in an accelerator solution with the mass fraction of 0.1-10% for 0.5-5 minutes before the polyacrylonitrile protofilament enters a pre-oxidation furnace for pre-oxidation.
The invention also provides a use method of the polyacrylonitrile-based carbon fiber precursor preoxidation accelerant, wherein the polyacrylonitrile-based carbon fiber precursor stays in an accelerant solution with the mass fraction of 0.1-10% for 0.5-5 minutes before entering a preoxidation furnace for preoxidation treatment.
The solvent in the accelerator solution is an organic or inorganic solvent which can not dissolve the polypropionitrile, the organic solvent is ethanol or acetone, and the inorganic solvent is water.
The invention has the advantages and beneficial effects that:
the preoxidation accelerant is used in any one or more of the preparation of the polyacrylonitrile spinning solution, the spinning of the precursor and the preoxidation treatment, so that the preoxidation temperature of the polyacrylonitrile precursor is reduced by more than 10 ℃, the preoxidation time is shortened by more than 15%, the energy consumption in the carbon fiber preparation process is effectively reduced, the production efficiency is improved, and the method has the advantages of simple operation process, low cost, less investment, compatibility with the existing carbon fiber production equipment and the like.
Detailed Description
The present invention and its effects are described in further detail below with reference to examples, and it should be noted that the following examples are intended to facilitate understanding of the present invention without any limitation thereto.
Example 1
(1) Preparing polyacrylonitrile spinning solution: acrylonitrile by mass fraction: dimethyl sulfoxide: itaconic acid: azobisisobutyronitrile: cumene hydroperoxide 22: 100: 0.2: 0.1: 0.1, adding the mixture into a polymerization kettle, and carrying out polymerization reaction for 24 hours at 63 ℃ under the stirring condition; demonomerization and deaeration are carried out for 8 hours under the conditions that the vacuum degree is 0.01MPa and the temperature is 63 ℃ to obtain spinning solution.
(2) Spinning of protofilament: and conveying the spinning solution to a 3K spinneret plate with the aperture of 65 micrometers through a metering pump for wet spinning, and winding after solidification, drafting, washing, oiling and heat setting to obtain the polyacrylonitrile precursor.
(3) Pre-oxidation: carrying out gradient temperature rise pre-oxidation treatment of 3 temperature zones on the polyacrylonitrile protofilament obtained in the step 3) in an air atmosphere, wherein the pre-oxidation treatment temperatures are 220, 240 and 260 ℃, the retention time of the fiber in each temperature zone is 20 minutes, and the total pre-oxidation treatment time is 60 minutes.
Example 2
(1) Preparing polyacrylonitrile spinning solution: acrylonitrile by mass fraction: dimethyl sulfoxide: itaconic acid: azobisisobutyronitrile ═ 22: 100: 0.2: 0.1, adding the mixture into a polymerization kettle, and carrying out polymerization reaction for 24 hours at 63 ℃ under the stirring condition; demonomerization and deaeration are carried out for 8 hours under the conditions that the vacuum degree is 0.01MPa and the temperature is 63 ℃ to obtain spinning solution.
(2) Preparation of immersion liquid: the tert-butyl hydroperoxide was prepared into an aqueous solution having a mass concentration of 2%, and placed in an immersion tank.
(3) Spinning of protofilament: conveying the spinning solution to a 3K spinneret plate with the aperture of 65 microns through a metering pump for wet spinning, and winding after solidification, drafting, washing, dipping, oiling and heat setting to obtain polyacrylonitrile protofilament, wherein the retention time of the fiber in a dipping tank is 4 seconds;
(4) pre-oxidation: and (4) carrying out gradient temperature rise pre-oxidation treatment on the polyacrylonitrile protofilament obtained in the step (3) in a 4-temperature zone in an air atmosphere, wherein the pre-oxidation treatment temperature is respectively 200, 220, 240 and 260 ℃, the retention time of the fiber in each temperature zone is 15 minutes, and the total pre-oxidation treatment time is 60 minutes.
Example 3
(1) Preparing polyacrylonitrile spinning solution: the same as in example 2.
(2) Preparation of immersion liquid: dicumyl peroxide is prepared into an acetone solution with the mass concentration of 3%, and the acetone solution is placed in an impregnation tank.
(3) Spinning of protofilament: and conveying the spinning solution to a 3K spinneret plate with the aperture of 65 micrometers through a metering pump for wet spinning, and winding after solidification, drafting, washing, oiling and heat setting to obtain the polyacrylonitrile precursor.
(4) Pre-oxidation: dipping the polyacrylonitrile protofilament in the step (3) in the dipping solution in the step (2) for 2 minutes; the impregnated polyacrylonitrile protofilament directly enters a pre-oxidation furnace, and is subjected to 4-temperature-zone gradient heating pre-oxidation treatment under the air atmosphere, wherein the pre-oxidation treatment temperatures are 190, 220, 240 and 270 ℃, the retention time of the fiber in each temperature zone is 10 minutes, and the total pre-oxidation treatment time is 40 minutes.
Example 4
(1) Preparing polyacrylonitrile spinning solution: the same as in example 2.
(2) Preparation of immersion liquid: preparing the di-tert-butyl peroxide into an ethanol solution with the mass concentration of 5%, and placing the ethanol solution into an impregnation tank.
(3) Spinning of protofilament: the same as in example 2.
(4) Pre-oxidation: dipping the polyacrylonitrile protofilament in the step (3) in the dipping solution in the step (2) for 1 minute; and (3) directly feeding the impregnated polyacrylonitrile protofilament into a pre-oxidation furnace, and performing gradient heating pre-oxidation treatment in a 3-temperature zone under the air atmosphere, wherein the pre-oxidation treatment temperatures are 220, 240 and 265 ℃, the retention time of the protofilament in each temperature zone is 15 minutes, and the total pre-oxidation treatment time is 45 minutes.
Comparative example
(1) The preparation conditions of the polyacrylonitrile protofilament are the same as example 1, but cumene hydroperoxide is not generated in the polymerization formula;
(2) carrying out 6-temperature-zone gradient heating pre-oxidation treatment on polyacrylonitrile protofilament in an air atmosphere, wherein the pre-oxidation treatment temperature is respectively 200, 220, 240, 260, 270 and 280 ℃, the residence time of the protofilament in each temperature zone is 12 minutes, and the total pre-oxidation treatment time is 72 minutes.
The degree of pre-oxidation of polyacrylonitrile fibers can be characterized by the density of the fibers, the higher the density of pre-oxidized fibers, the higher the degree of pre-oxidation. The densities of the pre-oxidized fibers obtained in examples and comparative examples were measured by a density gradient tube method, and the results are shown in Table 1. The use of a pre-oxidation promoter effectively reduces the pre-oxidation temperature and pre-oxidation time, with substantially equivalent pre-oxidation levels of the pre-oxidized fibers obtained.
TABLE 1
Claims (10)
1. The application of the peroxide as the preoxidation accelerant of the polyacrylonitrile-based carbon fiber precursor is characterized in that: in the preparation process of the polyacrylonitrile spinning solution, cumene hydroperoxide is used as a pre-oxidation promoter, the peroxide can reduce the pre-oxidation temperature of precursor, the half-life period is 1-60 minutes at 200 ℃, the pre-oxidation refers to the step of carrying out 3-temperature-zone gradient heating pre-oxidation treatment under the air atmosphere, the pre-oxidation treatment temperatures are 220, 240 and 260 ℃, and the total pre-oxidation treatment time is 60 minutes.
2. The application of the peroxide as the preoxidation accelerant of the polyacrylonitrile-based carbon fiber precursor is characterized in that: in the spinning process of the protofilament, tert-butyl hydroperoxide is used as a pre-oxidation promoter, the peroxide can reduce the pre-oxidation temperature of the protofilament, the half-life period is 1-60 minutes at 200 ℃, the pre-oxidation is performed by adopting gradient temperature rise pre-oxidation treatment of a 4-temperature zone, the pre-oxidation treatment temperatures are 200, 220, 240 and 260 ℃, and the total pre-oxidation treatment time is 60 minutes.
3. The application of the peroxide as the preoxidation accelerant of the polyacrylonitrile-based carbon fiber precursor is characterized in that: dicumyl peroxide is used as a pre-oxidation promoter in the pre-oxidation treatment process, the pre-oxidation temperature of the protofilament can be reduced by the peroxide, the half life period is 1-60 minutes at 200 ℃, the pre-oxidation is performed by adopting gradient temperature rise pre-oxidation treatment of a 4-temperature zone, the pre-oxidation treatment temperatures are respectively 190 ℃, 220 ℃, 240 ℃ and 270 ℃, and the total pre-oxidation treatment time is 40 minutes.
4. The application of the peroxide as the preoxidation accelerant of the polyacrylonitrile-based carbon fiber precursor is characterized in that: the method is characterized in that di-tert-butyl peroxide is used as a pre-oxidation accelerator in pre-oxidation treatment, the peroxide can reduce the pre-oxidation temperature of protofilaments, the half life period is 1-60 minutes at 200 ℃, the pre-oxidation is performed by adopting gradient temperature rise pre-oxidation treatment of a 3-temperature zone, the pre-oxidation treatment temperatures are respectively 220 ℃, 240 ℃ and 265 ℃, and the total pre-oxidation treatment time is 45 minutes.
5. The use of claim 1, wherein the preparation of the polyacrylonitrile spinning solution is to add a pre-oxidation promoter into an acrylonitrile polymerization formula, and the mass of the pre-oxidation promoter accounts for 0.1-5% of that of an acrylonitrile monomer or polyacrylonitrile.
6. The use of the fiber filament as claimed in claim 2, wherein the use of the fiber filament in spinning is that the fiber is solidified, drawn, washed with water, oiled and heat-set, and then stays in an accelerator solution with the mass fraction of 0.1-10% for 0.1-5 seconds.
7. The use according to claim 3 or 4, characterized in that the pre-oxidation treatment is carried out by allowing polyacrylonitrile precursor to stay in an accelerator solution with a mass fraction of 0.1-10% for 0.5-5 minutes before entering a pre-oxidation furnace for pre-oxidation.
8. Use according to claim 6, characterized in that: the solvent in the accelerator solution is an organic or inorganic solvent which can not dissolve polyacrylonitrile.
9. Use according to claim 7, characterized in that: the solvent in the accelerator solution is an organic or inorganic solvent which can not dissolve polyacrylonitrile.
10. Use according to claim 8 or 9, characterized in that: the organic solvent is ethanol and acetone, and the inorganic solvent is water.
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| CN102704043B (en) * | 2012-06-20 | 2014-07-09 | 北京化工大学 | Preparation method of polyacrylonitrile pre-oxidation fiber and carbon fiber |
| CN103572411B (en) * | 2012-07-31 | 2015-09-23 | 金发科技股份有限公司 | polyacrylonitrile-based carbon fibre, preparation method and application thereof |
| KR102322305B1 (en) * | 2013-12-23 | 2021-11-05 | 사이텍 인더스트리스 인코포레이티드 | Polyacrylonitrile (pan) polymers with low polydispersity index (pdi) and carbon fibers made therefrom |
| JP2016113726A (en) * | 2014-12-16 | 2016-06-23 | 東レ株式会社 | Polyacrylonitrile-based carbon fiber precursor fiber and carbon fiber production method |
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