CN114540990A - Pre-oxidation reaction control method of large-tow PAN (polyacrylonitrile) precursor - Google Patents
Pre-oxidation reaction control method of large-tow PAN (polyacrylonitrile) precursor Download PDFInfo
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- CN114540990A CN114540990A CN202210340837.5A CN202210340837A CN114540990A CN 114540990 A CN114540990 A CN 114540990A CN 202210340837 A CN202210340837 A CN 202210340837A CN 114540990 A CN114540990 A CN 114540990A
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- Prior art keywords
- tow
- oxidation
- pan
- carbon fiber
- small
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002243 precursor Substances 0.000 title claims abstract description 10
- 229920002239 polyacrylonitrile Polymers 0.000 title description 31
- 239000004917 carbon fiber Substances 0.000 claims abstract description 39
- 230000003647 oxidation Effects 0.000 claims abstract description 27
- 230000008646 thermal stress Effects 0.000 claims abstract description 19
- 238000002166 wet spinning Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000000578 dry spinning Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 230000035882 stress Effects 0.000 claims 1
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000835 fiber Substances 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a pre-oxidation reaction control method of a large tow PAN precursor, which belongs to the technical field of carbon fiber preparation, and comprises the steps of firstly measuring the thermal stress of a small tow PAN precursor with a stable pre-oxidation process, then carrying out continuous pre-oxidation treatment on the large tow PAN fiber, wherein the pre-oxidation temperature is 180-300 ℃, and regulating and controlling the temperature of each pre-oxidation temperature zone on the basis of the small tow pre-oxidation process, so that the deviation of the thermal stress of each pre-oxidation temperature zone of the large tow and the thermal stress of the corresponding small tow is within plus or minus 5%. The tensile strength of the large-tow carbon fiber prepared by the method is equivalent to that of the corresponding small-tow carbon fiber, and the ratio of the tensile strength of the large-tow carbon fiber to the tensile strength of the corresponding small-tow carbon fiber is 0.90-1.20.
Description
The technical field is as follows: the invention belongs to the technical field of carbon fiber preparation, and relates to a control method for a pre-oxidation reaction of large-tow carbon fibers.
Technical background: large tow carbon fibers play an extremely important role in modern emerging industries, leading carbon fiber technology and market development. However, large tow carbon fibers have inherent mass and heat transfer problems during the manufacturing process, making large tow carbon fibers inferior in performance to small tow carbon fibers. On one hand, the mass and heat transfer problems of the large-tow PAN fiber are particularly obvious in the pre-oxidation process, the heat conduction efficiency is low, the skin-core structure of local overheating and gas-solid phase reaction in the tow occurs simultaneously, the mechanical property of the large-tow carbon fiber is often inferior to that of the small-tow carbon fiber, and the application space of the large-tow carbon fiber in the high-end field is limited. On the other hand, the thermo-chemical reaction of the PAN fiber can cause the synchronous response of the thermal stress of the PAN fiber, and in order to solve the problem of heat release control in the pre-oxidation process of the large-tow PAN fiber, the heat release process of the large-tow PAN fiber is regulated and controlled by adjusting the thermal stress level of the large-tow PAN fiber in the pre-oxidation process to be the same as or close to the thermal stress of the corresponding small-tow PAN fiber from the angle of the thermal stress, so that the high-performance large-tow carbon fiber with the same level as the mechanical property of the small-tow carbon fiber is prepared.
The invention content is as follows: the invention provides a pre-oxidation reaction control method of large tow PAN precursor, which aims to control the pre-oxidation heat release of large tow PAN fiber and prepare high-performance large tow carbon fiber.
In order to realize the invention, the technical scheme is as follows:
a pre-oxidation reaction control method of large tow PAN precursor specifically comprises the following steps:
(1) firstly, the thermal stress (sigma) of each temperature zone of the high-performance small-tow carbon fiber preoxidation is obtained on a continuous preoxidation deviceS)；
(2) Based on the pre-oxidation process of the high-performance small-tow carbon fiber, the large-tow PAN fiber is operated on a pre-oxidation device, and the thermal stress (sigma) of the large-tow PAN fiber is controlled by adjusting the pre-oxidation temperatureL) The deviation between the preoxidation thermal stress of the large tow PAN and the thermal stress of the small tow PAN fiber in the corresponding temperature zone is within 5 percent, namely sigmaL/σS＝0.95～1.05。
The number of the large-tow carbon fibers is more than or equal to 36K, the pre-oxidation heat release can be well controlled by the pre-oxidation method, the tensile property of the finally obtained large-tow carbon fibers is equivalent to that of the corresponding small-tow PNA-based carbon fibers, and the tensile strength ratio TS of the large-tow carbon fibers to the small-tow PNA-based carbon fibers is equal to that of the small-tow PNA-based carbon fibersL/TSS0.9 to 1.2.
The above-described pre-oxidation control scheme, which creatively associates thermal stress with the pre-oxidation reaction, has the following advantages:
1. the mechanical property of the large-tow carbon fiber reaches the mechanical level of the small-tow carbon fiber, and the method is suitable for the application field of the small-tow carbon fiber.
2. The method is easy to operate, simple and effective, and has good matching property with continuous production devices of enterprises.
The specific implementation mode is as follows:
for purposes of making the present invention more apparent in light of the objects, aspects and advantages thereof, the present invention is further described in connection with the following examples, it being understood that the specific examples set forth herein are intended to be illustrative only and are not intended to be limiting.
Comparative example: the pre-oxidation temperature of the four temperature zones of the 48K large tow PAN fiber and the 12K small tow PAN fiber are kept the same, the pre-oxidation time of each temperature zone is 15min, and the pre-oxidation thermal stress ratio and the final carbon fiber tensile strength are shown in the following table.
| Categories | 12K-PAN | 48K-PAN | σL/σSOr TSL/TSS |
| Pre-oxidation temperature 1 | 220 | 220 | 1.07 |
| Pre-oxidation temperature 2 | 235 | 235 | 1.08 |
| Pre-oxidation temperature 3 | 250 | 250 | 1.10 |
| PreoxidationTemperature 4 | 265 | 265 | 1.25 |
| Tensile strength Ts of carbon fiber | 4.0GPa | 3.4GPa | 0.85 |
Example 1: the 48K large-tow wet spinning PAN fiber is pre-oxidized in four temperature zones for 15min, the thermal stress ratio of each temperature zone is controlled to be 1.0/1.01/0.99/0.98 respectively on the basis of the corresponding small-tow temperature process, the temperature of the corresponding pre-oxidation temperature zone is reduced by 2 ℃/2 ℃/2 ℃/4 ℃ respectively, and the tensile strength of the finally prepared large-tow carbon fiber is shown in the following table.
| Categories | 12K-PAN | 48K-PAN | σL/σSOr TSL/TSS |
| Pre-oxidation temperature 1 | 220 | 218 | 1.0 |
| Pre-oxidation temperature 2 | 235 | 233 | 1.01 |
| Pre-oxidation temperature 3 | 250 | 248 | 0.99 |
| Pre-oxidation temperature 4 | 265 | 261 | 0.98 |
| Tensile strength Ts of carbon fiber | 4.0GPa | 4.2GPa | 1.05 |
Example 2: the PAN fiber for dry-jet wet spinning of the 48K large tows is pre-oxidized in three temperature zones for 20min, the thermal stress ratio of each temperature zone is controlled to be 0.98/0.98/0.99 respectively on the basis of the process corresponding to the temperature of the small tows, the temperature of the corresponding pre-oxidation temperature zone is reduced by 2 ℃/3 ℃/4 ℃ respectively, and the tensile strength of the finally prepared large-tow carbon fiber is shown in the following table.
| Categories | 12K-PAN | 48K-PAN | σL/σSOr TSL/TSS |
| Pre-oxidation temperature 1 | 240 | 238 | 1.0 |
| Pre-oxidation temperature 2 | 251 | 248 | 0.99 |
| Pre-oxidation temperature 3 | 262 | 258 | 0.99 |
| Tensile strength Ts of carbon fiber | 5.4GPa | 5.0GPa | 0.926 |
Example 3: the 36K large-tow dry spinning PAN fiber is pre-oxidized in six temperature zones for 10min, the thermal stress ratio of each temperature zone is controlled to be 1.02/1.0/0.99/0.99/0.99 respectively on the basis of the corresponding small-tow temperature process, the temperature of the corresponding pre-oxidation temperature zone is reduced by 2 ℃/2 ℃/2 ℃/4 ℃, and the tensile strength of the finally prepared large-tow carbon fiber is shown in the following table.
| Categories | 8K-PAN | 36K-PAN | σL/σSOr TSL/TSS |
| Pre-oxidation temperature 1 | 254 | 255 | 1.02 |
| Pre-oxidation temperature 2 | 258 | 257 | 1.0 |
| Pre-oxidation temperature 3 | 263 | 261 | 0.99 |
| Pre-oxidation temperature 4 | 268 | 265 | 0.99 |
| Pre-oxidation temperature 5 | 270 | 267 | 0.99 |
| Pre-oxidation temperature 6 | 272 | 269 | 0.99 |
| Tensile strength Ts of carbon fiber | 3.8GPa | 3.7GPa | 0.97 |
Claims (7)
1. A pre-oxidation reaction control method of large tow PAN precursor is based on a thermal stress control principle and based on a pre-oxidation process of small tow PAN precursor, the thermal reaction stress (sigma) of the large tow PAN precursor is controlledL) Thermal stress (sigma) of small tow precursor corresponding to polymerization spinning methodS) Deviation is controlled within plus or minus 5%, i.e. sigmaL/σS0.95-1.05, and the Tensile Strength (TS) of the finally prepared large-tow carbon fiberL) And Tensile Strength (TS) of small-tow carbon fiberS) Equivalent, the ratio of the two TSL/TSS0.90 to 1.20.
2. The method of claim 1, wherein the thermal stress is a tensile force per unit cross-sectional area of the tow in MPa.
3. The method of claim 1, wherein the pre-oxidation temperature zone is 180 ℃ to 300 ℃.
4. The method of claim 1, wherein the temperature adjustment for each temperature zone of the pre-oxidation is less than or equal to 8 ℃.
5. The method of claim 1, wherein the pre-oxidation time per temperature zone is 30min or less, and the number of pre-oxidation temperature zones is 6 or less.
6. The method of claim 1, wherein the PAN filament spinning method comprises wet spinning, dry jet wet spinning, and dry spinning.
7. The method of claim 1, wherein the K number of PAN filaments of the large tow is not less than 36K.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210340837.5A CN114540990B (en) | 2022-03-25 | 2022-03-25 | Pre-oxidation reaction control method for large-tow PAN precursor |
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| CN202210340837.5A CN114540990B (en) | 2022-03-25 | 2022-03-25 | Pre-oxidation reaction control method for large-tow PAN precursor |
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| CN114540990A true CN114540990A (en) | 2022-05-27 |
| CN114540990B CN114540990B (en) | 2024-02-02 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120027944A1 (en) * | 2009-03-31 | 2012-02-02 | Muhuo Yu | Processes for producing carbon fiber, the filament thereof, and pre-oxidized fiber |
| CN111218733A (en) * | 2020-03-13 | 2020-06-02 | 北京化工大学 | Preparation method of large-diameter high-strength medium-modulus carbon fiber |
| CN111560666A (en) * | 2020-06-17 | 2020-08-21 | 江苏恒神股份有限公司 | Pre-oxidation method of polyacrylonitrile-based carbon fiber precursor |
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- 2022-03-25 CN CN202210340837.5A patent/CN114540990B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120027944A1 (en) * | 2009-03-31 | 2012-02-02 | Muhuo Yu | Processes for producing carbon fiber, the filament thereof, and pre-oxidized fiber |
| CN111218733A (en) * | 2020-03-13 | 2020-06-02 | 北京化工大学 | Preparation method of large-diameter high-strength medium-modulus carbon fiber |
| CN111560666A (en) * | 2020-06-17 | 2020-08-21 | 江苏恒神股份有限公司 | Pre-oxidation method of polyacrylonitrile-based carbon fiber precursor |
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