CN108823683A - Polyacrylonitrile carbon fiber and preparation method thereof - Google Patents
Polyacrylonitrile carbon fiber and preparation method thereof Download PDFInfo
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- CN108823683A CN108823683A CN201810739311.8A CN201810739311A CN108823683A CN 108823683 A CN108823683 A CN 108823683A CN 201810739311 A CN201810739311 A CN 201810739311A CN 108823683 A CN108823683 A CN 108823683A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
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Abstract
The invention discloses polyacrylonitrile carbon fibers and preparation method thereof, wherein the method includes：(1) using dimethyl sulfoxide or dimethylformamide as solvent, acrylonitrile and itaconic acid or acrylonitrile and methyl acrylate and itaconic acid are subjected to combined polymerization, to obtain polymer spinning solution；(2) polymer spinning solution is successively carried out to spinning, drawing-off, washes, oil, drying and thermal finalization, to obtain polyacrylonitrile fibril；(3) polyacrylonitrile fibril is successively carried out to pre-oxidation and carbonization treatment, obtain polyacrylonitrile carbon fiber, wherein the preoxidation process includes low temperature pre-oxidation and high temperature pre-oxidation, the low temperature pre-oxidation carries out in air atmosphere, and the high temperature pre-oxidation carries out in nitrogen atmosphere.Using carbon fiber tensile strength made from this method be higher than 4.9GPa, stretch modulus be higher than 230MPa, and with merely in the carbon fiber that air atmosphere pre-oxidation treatment obtains compared with, volume density increase by 1.6%, fiber yield increase by 5.6%.
Description
Technical field
The invention belongs to carbon material technical fields, specifically, the present invention relates to polyacrylonitrile carbon fiber and its preparation sides
Method.
Background technique
Carbon fiber has high specific strength, high ratio modulus characteristic, and has high temperature resistance under an inert atmosphere, keeps it wide
It is general to be applied to the fields such as Aeronautics and Astronautics, automobile, chemical industry, the energy, sports equipment.
Polyacrylonitrile (PAN) carbon fiber is the important carbon fiber kind of one kind for realizing industrialized production, and preparation process is main
Including processes such as polymerization, precursor spinning, pre-oxidation and carbonizations.Preoxidation process is the process taken over from the past and set a new course for the future, in air atmosphere and
Under certain tension force effect, PAN precursor is subjected to 200-300 DEG C of pre-oxidation treatment, and it is a series of multiple that cyclisation, dehydrogenation and oxidation etc. occurs
The linear molecule of miscellaneous reaction, PAN changes to the trapezium structure of Heat-resistant stable, and the fiber by pre-oxidation treatment is in subsequent high temperature carbon
Change process, which is not melted, not to be melted, and fibre morphology is still kept.
In order to accelerate pre-oxidation, more stable cross-linked network structure is formed, polyacrylonitrile fibre preoxidation process is logical
It is often carried out in the air containing oxygen, and increases Pre oxidation and can be improved pre-oxidation speed.Oxygen element participates in
Pre-oxidation, both formed cyclized structure or formed containing oxide structure, and be more than certain Pre oxidation, although can improve in advance
Oxygen cyclized structure, but excessive oxidation structure is unavoidably generated, because oxidation reaction speed at this time is greater than cyclization speed.
Prepare raw material-acrylonitrile of PAN carbon fiber, carbon content rate is 68% or so, but acrylonitrile by polymerization, spinning,
Pre-oxidation and carbonization, are finally changed into carbon fiber, and in addition to non-carbon element removes, carbon can also be lost, at this stage fiber yield
About 55%.The final structure of carbon fiber is referred to as random graphits structure or graphite-like structure, oxygen member in fiber in carbonisation
Carbon atom is taken away in element evolution, and evolution forms vacancy defect, and there are incomplete six-membered ring structure, these vacancy defects for fibrous matrix
So that fibre structure compactness reduces, the rate of recovery of carbon in the performance and raw material of carbon fiber finally will affect.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of polyacrylonitrile carbon fibers and preparation method thereof, using the party
Carbon fiber tensile strength made from method be higher than 4.9GPa, stretch modulus be higher than 230MPa, and with merely in the pre- oxygen of air atmosphere
The carbon fiber that change is handled is compared, and volume density increases by 1.6%, and fiber yield increases by 5.6%.
In one aspect of the invention, the invention proposes a kind of methods for preparing polyacrylonitrile carbon fiber.According to this hair
Bright embodiment, the method includes：(1) using dimethyl sulfoxide or dimethylformamide as solvent, by acrylonitrile and itaconic acid
Or acrylonitrile carries out combined polymerization with methyl acrylate and itaconic acid, to obtain polymer spinning solution；(2) by polymer spinning
Solution successively carries out spinning, drawing-off, washes, oils, drying and thermal finalization, to obtain polyacrylonitrile fibril；(3) by polypropylene
Nitrile precursor successively carries out pre-oxidation and carbonization treatment, obtains polyacrylonitrile carbon fiber, wherein the preoxidation process includes low temperature
Pre-oxidation and high temperature pre-oxidation, the low temperature pre-oxidation carry out in air atmosphere, and the high temperature pre-oxidation is in nitrogen atmosphere
It carries out.
Preferably, the temperature of the low temperature pre-oxidation is not higher than 265 degrees Celsius.
Preferably, the temperature of the low temperature pre-oxidation is 200~265 degrees Celsius.
Preferably, the low temperature pre-oxidation is carried out using gradient increased temperature.
Preferably, the time of the low temperature pre-oxidation is 45~100 minutes.
Preferably, the temperature of the high temperature pre-oxidation is 265~315 degrees Celsius.
Preferably, the temperature of the high temperature pre-oxidation is 280~300 degrees Celsius.
Preferably, the time of the high temperature pre-oxidation is 5~20 minutes.
In another aspect of the invention, the invention proposes a kind of carbon fibers.According to an embodiment of the invention, the carbon
Fiber is prepared using method described above.
Inventor is by largely attempting discovery, and in order to form stable pre- oxide structure, pre-oxidation must reach certain temperature,
But it will form excessive oxidation structure in oxidizing atmosphere, and the generation of excessive oxidation structure reduces the thermostabilization of preoxidized fiber
Property, thermal cracking, which occurs, in carbonization causes mass loss, largely affects the carbon yield of PAN fiber, and produce in fiber
Raw defect, influences carbon fiber mechanical property.
The present invention by change pre-oxidation hot stage reaction atmosphere, inhibit pre-oxidized fibers oxidation structure formation and
Pre-oxidized fibers cyclized structure is improved, to form pre- oxide structure preferably.Due to there is no excessive oxidation in preoxidized fiber
Structure does not have a large amount of oxygen element combination carbon to form oxycarbide evolution in high temperature cabonization, carbon yield on the one hand can be improved, separately
On the one hand defect will not be generated in fiber and improve carbon fiber compactness.The high-strength carbon fiber for taking the technology to prepare stretches
Intensity is more than 4.9GPa, and stretch modulus is in 230GPa or more.With the carbon fiber phase obtained in air atmosphere pre-oxidation treatment merely
Than volume density increases by 1.6%, and carbon yield increases by 5.6%.
Detailed description of the invention
Fig. 1 is the method flow schematic diagram for preparing polyacrylonitrile carbon fiber；
Fig. 2A is the preoxidation process schematic diagram of 1-2 of the embodiment of the present invention；
Fig. 2 B is the preoxidation process schematic diagram of 3-4 of the embodiment of the present invention；
Fig. 3 is the preoxidation process schematic diagram of comparative example.
Specific embodiment
Below by conjunction with the embodiments and its Fig. 1 the invention will be further described, following embodiment be it is descriptive,
It is not restrictive, this does not limit the scope of protection of the present invention.
In one aspect of the invention, the invention proposes a kind of methods for preparing polyacrylonitrile pre-oxidation fiber.According to this
The embodiment of invention, with reference to Fig. 1, this method includes：
S1：Using dimethyl sulfoxide or dimethylformamide as solvent, by acrylonitrile and itaconic acid or acrylonitrile and acrylic acid
Methyl esters and itaconic acid carry out combined polymerization
In the step, using dimethyl sulfoxide or dimethylformamide as solvent, by acrylonitrile and itaconic acid or acrylonitrile with
Methyl acrylate and itaconic acid carry out combined polymerization, to obtain polymer spinning solution.Specifically, during being somebody's turn to do, with dimethyl
Sulfoxide (DMSO) or dimethylformamide (DMF) are solvent, at 60~70 DEG C, with azo-bis-isobutyl cyanide at a temperature of preferably 65 DEG C
(AIBN) acrylonitrile, itaconic acid binary solution or acrylonitrile, methyl acrylate, the copolymerization of itaconic acid ternary solution are carried out for initiator
It closes, reacts 12~36 hours, preferably 24 hours, obtain polymer spinning solution, wherein acrylonitrile, methyl acrylate and clothing health
The mass ratio of acid is (90~99.5):(0~7):(0.5~5).Then in the case of stirring, in 60~70 DEG C, preferably 65
DEG C, vacuum degree be greater than 0.095MPa under the conditions of remove polymer spinning solution in unreacted monomer, preferably 8 hours 7~9 hours
Stop stirring, the standing and defoaming under 55~65 DEG C preferably 60 DEG C same vacuum conditions afterwards.
S2：Polymer spinning solution is successively carried out to spinning, drawing-off, washes, oil, drying and thermal finalization prepares polypropylene
Nitrile precursor
In the step, polymer spinning solution obtained above is successively carried out to spinning, drawing-off, wash, oil, drying and
Thermal finalization, to obtain polyacrylonitrile fibril.Specifically, during being somebody's turn to do, with mass concentration for 60-80% dimethyl sulfoxide
(DMSO) aqueous solution is coagulating bath, preferably 70%DMSO aqueous solution, and at 20~65 DEG C, coagulation forming at a temperature of preferably 45 DEG C gathers
It closes object spinning solution and is changed into as-spun fibre, it is 40%, 20%DMSO water that as-spun fibre successively passes through mass concentration at room temperature again
Solution continues to solidify.Then 4~7 times of drawing-off, preferably 5 times in boiling water, is washed, the fibre after washing in 50~90 DEG C of water of temperature
Dimension oils, dries, 2~3.2 times of drawing-off, preferably 2.4 times in overheated steam, most obtains polyacrylonitrile original through thermal finalization afterwards
Silk.
S3：Polyacrylonitrile fibril is successively carried out to pre-oxidation and carbonization treatment
In the step, polyacrylonitrile fibril obtained above is subjected to low temperature pre-oxidation in air atmosphere first, then
High temperature pre-oxidation is carried out in a nitrogen atmosphere, is finally carried out carbonization treatment, is finally obtained polyacrylonitrile carbon fiber.On specifically,
It states polyacrylonitrile fibril and is introduced into not higher than 265 DEG C (preferably 200~265 DEG C Gradients heating) air atmosphere pre-oxidation furnaces and carry out
Low temperature pre-oxidation is handled 45~100 minutes, then enters back into 265~315 DEG C of (preferably 280~300 DEG C) nitrogen atmosphere pre-oxidation furnaces
Middle processing 5~20 minutes, finally enters and carries out carbonization treatment in carbide furnace.Inventors have found that under the conditions of not higher than 265 DEG C, with
The raising of temperature, pre-oxidation cyclized structure increase than oxidation structure it is more, and in the high temperature pre-oxidizing stage of the application, pre- oxygen
Cyclisation, dehydrogenation and cross-linking reaction only occur for fiber, without oxidation reaction, and heat scission reaction will not occur, thus
Control polyacrylonitrile pre-oxidation fiber oxidation structure content.
Pre-oxidation treatment is carried out in single air atmosphere in the past, uses air and high-temperature process to improve pre-oxidation rate
Pre- oxidation stability structure is formed, unavoidably will form excessive oxidation structure in preoxidized fiber, and the life of excessive oxidation structure
At the thermal stability for reducing preoxidized fiber, thermal cracking occurs in carbonization and causes mass loss, largely affects PAN fiber
Carbon yield, and generate defect in fiber, influence carbon fiber mechanical property.The present invention is by changing pre-oxidation treatment high temperature section
Then atmosphere carries out high temperature that is, so that polyacrylonitrile fibril first carries out low temperature pre-oxidation in air atmosphere in nitrogen atmosphere
Pre-oxidation makes preoxidized fiber that cyclisation, dehydrogenation and cross-linking reaction only occur in high temperature pre-oxidizing stage, without oxidation reaction,
To control polyacrylonitrile pre-oxidation fiber oxidation structure content, and then high temperature cabonization is reduced since oxygen escapes and oxygen evolution takes away
Carbon takes the technology that carbon yield can be greatly improved compared with conventional pre-oxidation process, and high high-strength of volume density can be obtained
Type carbon fiber, it is more than 4.9GPa that tensile strength, which can be obtained, after preoxidized fiber carbonization, and stretch modulus is in the high-strength of 230GPa or more
Type carbon fiber.With merely in the carbon fiber that air atmosphere pre-oxidation treatment obtains compared with, volume density increase by 1.6%, carbon yield increase
Add 5.6%.
In another aspect of the invention, the invention proposes a kind of carbon fibers.According to an embodiment of the invention, the carbon fiber
Dimension is prepared using method described above.As a result, by using the above method, obtained carbon fiber tensile strength is super
4.9GPa is crossed, stretch modulus is in 230GPa or more.With merely in the carbon fiber that air atmosphere pre-oxidation treatment obtains compared with, body is close
Degree increases by 1.6%, and carbon yield increases by 5.6%.It should be noted that above-mentioned be directed to prepares described by the method for polyacrylonitrile fibre
Feature and advantage be equally applicable to the carbon fiber, details are not described herein again.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
It is initiator with azodiisobutyronitrile (AIBN), with dimethyl sulfoxide (DMSO) for solvent, carries out acrylonitrile solution
Combined polymerization.In terms of the comonomer gross mass of investment, by acrylonitrile 97.2%, methyl acrylate 1.6% and itaconic acid 1.2%
Ratio puts into acrylonitrile monemer and comonomer methyl acrylate and itaconic acid into polymeric kettle, adds solvent DMSO, control
Monomers acrylonitrile accounts for the 22% of polymerization system gross mass, 65 DEG C at a temperature of react 24 hours, gained polymeric solution is through de- single
Deaeration carries out wet spinning.Spinning solution by metering pump, candle filter, the aperture 0.07mm spinneret, sequentially enter respectively by
The concentration that DMSO and water form is 70% level-one coagulating bath (temperature is 45 DEG C), concentration is 40% second level coagulating bath (room temperature) and dense
Degree forms in 20% three-level coagulating bath (room temperature), to carry out multistage at fibre；Completely molding after, by boiling water preliminary draft, washing,
The hot-rolling that oils is dry, and using overheated steam drawing-off again, secondary total draft control obtains polyacrylonitrile through thermal finalization at 12 times
Precursor, precursor fiber number are 1.2dtex.The precursor successively five pre- oxygen under 200,220,230,240,245 DEG C of air atmospheres
Low temperature pre-oxidation processing totally 100 minutes is carried out in furnace, using 280 DEG C nitrogen atmosphere high temperature pre-oxidation treatment 20 minutes, obtain
Preoxidized fiber (refers to Fig. 2A)；Preoxidized fiber is first handled in the low temperature carbonization furnace under 350,800 DEG C of nitrogen atmosphere, is then existed
1100, it is handled in high temperature carbonization furnace under 1400 DEG C of nitrogen atmosphere, obtains carbon fiber.Carbon fiber synnema tensile strength is
4.96GPa, stretch modulus 232GPa, line density 0.0697g/m, volume density 1.811g/cm3。
Embodiment 2
Polymer spinning solution, polyacrylonitrile fibril are prepared according to embodiment 1, precursor fiber number is 1.2dtex.The precursor according to
Totally 50 points of low temperature pre-oxidation processing processing are carried out in secondary five pre-oxidation furnaces under 200,220,240,250,260 DEG C of air atmospheres
Clock, using 290 DEG C nitrogen atmosphere high temperature pre-oxidation treatment 10 minutes, obtain preoxidized fiber (with reference to Fig. 2A)；Preoxidized fiber is first
Low-temperature carbonization is handled under 350,800 DEG C of nitrogen atmosphere, then under 1100,1400 DEG C of nitrogen atmosphere at high temperature cabonization
Reason, obtains carbon fiber.Carbon fiber synnema tensile strength be 4.93GPa, stretch modulus 230GPa, line density 0.0703g/m,
Volume density is 1.813g/cm3。
Embodiment 3
Polymer spinning solution, polyacrylonitrile fibril are prepared according to embodiment 1, precursor fiber number is 1.2dtex.The precursor according to
Low temperature pre-oxidation processing totally 90 minutes is carried out in secondary five pre-oxidation furnaces under 200,220,240,250,255 DEG C of air atmospheres,
Using 300 DEG C nitrogen atmosphere high temperature pre-oxidation treatment 10 minutes, obtain preoxidized fiber (with reference to Fig. 2 B)；Preoxidized fiber first exists
350, low-temperature carbonization is handled under 800 DEG C of nitrogen atmosphere, and then high temperature cabonization is handled under 1100,1400 DEG C of nitrogen atmosphere,
Obtain carbon fiber.Carbon fiber synnema tensile strength is 5.13GPa, stretch modulus 243GPa, line density 0.0705g/m, body
Density is 1.812g/cm3。
Embodiment 4
Polymer spinning solution, polyacrylonitrile fibril are prepared according to embodiment 1, precursor fiber number is 1.2dtex.The precursor according to
Low temperature pre-oxidation is carried out in secondary five pre-oxidation furnaces under 200,220,240,250,265 DEG C of air atmospheres to handle 45 minutes, then
By 300 DEG C nitrogen atmosphere high temperature pre-oxidation treatment 5 minutes, obtain preoxidized fiber (with reference to Fig. 2 B)；Preoxidized fiber first
350, low-temperature carbonization is handled under 800 DEG C of nitrogen atmosphere, and then high temperature cabonization is handled under 1100,1400 DEG C of nitrogen atmosphere,
Obtain carbon fiber.Carbon fiber synnema tensile strength is 5.03GPa, stretch modulus 237GPa, line density 0.0706g/m, body
Density is 1.814g/cm3。
Comparative example
With azodiisobutyronitrile (AIBN) for initiator, dimethyl sulfoxide (DMSO) is solvent, and it is total to carry out acrylonitrile solution
Polymerization.It is put into 97.2% acrylonitrile of mass concentration, 1.6% methyl acrylate and 1.2% itaconic acid ratio into polymeric kettle single
Body acrylonitrile and comonomer methyl acrylate and itaconic acid, add solvent DMSO, and control monomers acrylonitrile accounts for polymerization system
Mass concentration be 22%, 65 DEG C at a temperature of react 24 hours, gained polymeric solution carries out Wet-spinning through de- single deaeration
Silk.Spinning solution is by metering pump, candle filter, the aperture 0.07mm spinneret, in the solidification being made of dimethyl sulfoxide and water
Gradient freeze forms in bath, and dimethyl sulfoxide concentration is respectively 75%, 40%, 20%, and coagulation bath temperature is respectively 45 DEG C, room
Temperature, room temperature；By boiling water preliminary draft, wash, the hot-rolling that oils drying, using overheated steam drawing-off again, secondary total draft control
System obtains polyacrylonitrile fibril, precursor fiber number 1.2dtex through thermal finalization at 12 times.The precursor successively 200,220,240,
250, pre-oxidation treatment totally 75 minutes (see Fig. 3) is successively carried out in lower six pre-oxidation furnaces of 265,280 DEG C of air atmospheres, 350,
Low-temperature carbonization is handled under 800 DEG C of nitrogen atmosphere, and high temperature cabonization is handled under 800-1600 DEG C of nitrogen atmosphere, gained carbon fiber
Synnema tensile strength is 4.90GPa, stretch modulus 230GPa, line density 0.066g/m, volume density 1.772g/cm3。
Embodiment 1-4 and the performance of polyacrylonitrile carbon fiber obtained by comparative example are as shown in table 1.
The performance of 1 carbon fiber of table and precursor
The above is only preferred embodiments of the invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as the protection scope that do not invent.
Claims (9)
1. a kind of method for preparing polyacrylonitrile carbon fiber, which is characterized in that including：
(1) using dimethyl sulfoxide or dimethylformamide as solvent, by acrylonitrile and itaconic acid or acrylonitrile and methyl acrylate
Combined polymerization is carried out with itaconic acid, to obtain polymer spinning solution；
(2) polymer spinning solution is successively carried out to spinning, drawing-off, washes, oil, drying and thermal finalization, to obtain poly- third
Alkene nitrile precursor；
(3) polyacrylonitrile fibril is successively carried out to pre-oxidation and carbonization treatment, obtains polyacrylonitrile carbon fiber,
Wherein, the preoxidation process includes low temperature pre-oxidation and high temperature pre-oxidation, and the low temperature pre-oxidation is in air atmosphere
It carries out, the high temperature pre-oxidation carries out in nitrogen atmosphere.
2. the method as described in claim 1, which is characterized in that the temperature of the low temperature pre-oxidation is not higher than 265 degrees Celsius.
3. method according to claim 1 or 2, which is characterized in that the temperature of the low temperature pre-oxidation is 200~265 Celsius
Degree.
4. the method as described in claim 1, which is characterized in that the low temperature pre-oxidation is carried out using gradient increased temperature.
5. the method as described in claim 1, which is characterized in that the time of the low temperature pre-oxidation is 45~100 minutes.
6. the method as described in claim 1, which is characterized in that the temperature of the high temperature pre-oxidation is 265~315 degrees Celsius.
7. method as described in claim 1 or 6, which is characterized in that the temperature of the high temperature pre-oxidation is 280~300 Celsius
Degree.
8. method according to claim 6 or 7, which is characterized in that the time of the high temperature pre-oxidation is 5~20 minutes.
9. a kind of carbon fiber, which is characterized in that the carbon fiber is prepared into using any one of claim 1-8 the method
It arrives.
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| CN109881280A (en) * | 2019-02-18 | 2019-06-14 | 北京化工大学 | A kind of preparation method of polyacrylonitrile fibre, preparation method and its carbon fiber |
| CN110607592A (en) * | 2019-08-16 | 2019-12-24 | 北京化工大学 | Method for preparing polyacrylonitrile-based thermo-oxidative stabilized fiber |
| CN111118671A (en) * | 2019-12-26 | 2020-05-08 | 长春工业大学 | Preparation method of 25k large-tow carbon fiber |
| CN112030270A (en) * | 2020-09-08 | 2020-12-04 | 北京北美红杉科技发展有限公司 | Process for preparing refractory carbon fibers |
| CN112708968A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Rapid pre-oxidation method of polyacrylonitrile-based carbon fiber precursor |
| CN112708967A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Pre-oxidation method of polyacrylonitrile-based fiber and preparation method of carbon fiber |
| CN114540988A (en) * | 2021-08-25 | 2022-05-27 | 台湾塑胶工业股份有限公司 | Method for producing carbon fiber |
| WO2022165903A1 (en) * | 2021-02-05 | 2022-08-11 | 天津工业大学 | Preparation method for polyacrylonitrile-based carbon fiber |
| CN115612171A (en) * | 2022-10-20 | 2023-01-17 | 华能阜新风力发电有限责任公司 | Low-energy-consumption wind power blade recovery method |
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| 徐盼盼: "影响PAN纤维热稳定性的预氧结构调控", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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