CN106222803B - Prepare the method for pre-oxidizing of large-tow carbon fiber - Google Patents
Prepare the method for pre-oxidizing of large-tow carbon fiber Download PDFInfo
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- CN106222803B CN106222803B CN201610517888.5A CN201610517888A CN106222803B CN 106222803 B CN106222803 B CN 106222803B CN 201610517888 A CN201610517888 A CN 201610517888A CN 106222803 B CN106222803 B CN 106222803B
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- 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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Abstract
The present invention relates to organic polymer field, specifically a kind of method for pre-oxidizing for preparing large-tow carbon fiber includes the following steps：Big tow polyacrylonitrile copolymer fibre is pre-oxidized in 180~280 DEG C of temperature ranges in air atmosphere, 60~90min is heat-treated using 3 sections of gradient increased temperature modes, temperature gradient is 15 ± 2 DEG C, oxidation furnace circulated air blast velocity control is in 6 ± 2m/s, under -2~2% draw ratio, it is 1.35 ± 0.02g/cm that density, which is made,3Pre-oxidized fibers.Using conventional silicon carbide condition：Under nitrogen protection, under -2~2% draw ratio, 3 ± 1.5min of low-temperature carbonization at 300~900 DEG C, by gained fiber, 3 ± 1.5min of high temperature cabonization, draw ratio are -5~0% at 1000~1500 DEG C.The present invention carrys out the perfect pre-oxidized fibers of preparation structure, to prepare high-performance large-tow carbon fiber by controlling Pre oxidation gradient, oxidation furnace circulation wind speed and obtained oxidization fiber density.
Description
Technical field
The present invention relates to Carbon Fiber Technology field, specifically a kind of method for pre-oxidizing for preparing large-tow carbon fiber.
Background technique
It is known that reinforcing fiber is the main material of composite material, high efficiency, low cost carbon fiber is to composite material light weight
Change has important facilitation.And reduce there are two the approach of carbon fiber cost, first is that improving and spinning using dry spray wet processing
Silk speed；Another kind is using large-tow carbon fiber.Domestic some carbon fiber manufacturers and institution of higher learning pass through independent development,
Breached it is dry squirt method processing key technology, and it is less to the processing key technical research of large-tow carbon fiber.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of pre-oxidation sides for preparing large-tow carbon fiber
Method, under the mode of 3 sections of gradient increased temperatures pre-oxidation, it is necessary to Pre oxidation gradient, oxidation furnace circulation wind speed and acquired
Oxidization fiber density controlled.If temperature gradient is too high or too low, easily cause excessively to pre-oxidize or pre-oxidize it is insufficient, it is unfavorable
In preparing high-performance carbon fibre, fiber can reasonably be controlled in preoxidation process by controlling oxidation furnace temperature gradient
Cyclization and oxidation reaction effectively avoid the generation of skin-core structure；Oxidation furnace recycles wind speed and big bunch fiber heat transfer
It is related with oxygen molecule diffusion, if wind speed is too small, it is easy to be formed in fiber and concentrates heat release and skin-core structure, defect is caused to increase,
If wind speed is too big, fibre bundle is easy share split in oxidation furnace, is unfavorable for operation stability；The size of oxidization fiber density reflects pre- oxygen
The size of change degree.The present invention by Pre oxidation gradient, oxidation furnace recycle wind speed and obtained oxidization fiber density into
Row control, carrys out the perfect pre-oxidized fibers of preparation structure, to prepare high-performance large-tow carbon fiber.
The present invention solve above-mentioned technical problem the technical solution adopted is that：A kind of pre-oxidation side preparing large-tow carbon fiber
Method includes the following steps：By big tow polyacrylonitrile copolymer fibre in air atmosphere in pre- in 180~280 DEG C of temperature ranges
Oxidation is heat-treated 60~90min using 3 sections of gradient increased temperature modes, and temperature gradient is 15 ± 2 DEG C, oxidation furnace circulated air wind speed control
System is in 6 ± 2m/s, and under -2~2% draw ratio, it is 1.35 ± 0.02g/cm that density, which is made,3Pre-oxidized fibers；Using normal
Advise Carbonization Conditions：Under nitrogen protection, under -2~2% draw ratio, 3 ± 1.5min of low-temperature carbonization at 300~900 DEG C, by institute
Fiber 3 ± 1.5min of high temperature cabonization at 1000~1500 DEG C is obtained, draw ratio is -5~0%.
The big tow polyacrylonitrile copolymer fibre is 24K.The big tow polyacrylonitrile copolymer fibre, which removes, contains third
It further include the copolymer of one or more following monomers outside alkene nitrile monomer：Itaconic acid, acrylic acid, methacrylic acid, metering system
Sour methyl esters, methyl acrylate.
The invention has the advantages that carrying out mechanical property characterization to prepared carbon fibre tow, the results showed that：?
In the big bunch fiber preoxidation process of 24K, circulation blast velocity control controls the temperature ladder of 3 sections of heat treatment in 6 ± 2m/s in oxidation furnace
Degree is 15 ± 2 DEG C, and it is 1.35 ± 0.02g/cm that density, which is made,3Pre-oxidized fibers, handled using low temperature and high temperature cabonization, institute
The tensile strength for obtaining carbon fiber is higher than 4.5GPa, and modulus is 240GPa or so.It is proved by example, by being followed in control oxidation furnace
The size of ring wind speed and temperature gradient, it will influence the structure and performance of pre-oxidized fibers and carbon fiber.Therefore, big in 24K
In bunch fiber preoxidation process, it can be come by recycling wind speed and temperature gradient in the oxidation furnace in control preoxidation process
It improves the structure of carbon fiber and improves its mechanical property, have good directive significance to inexpensive large-tow carbon fiber is prepared.
Specific embodiment
The present invention will be further described with reference to the examples below：
Embodiment 1：
Tuozhan Fiber Co., Ltd., Weihai's production for selecting wet process to spin, the PAN containing 90% or more acrylonitrile monemer component is total
Poly- fiber（Its tow is 24K, copolymer composition（wt%）For：Acrylonitrile（AN）:Methyl acrylate（MA）:Itaconic acid（IA）=96:
2.0:2.0）, in air dielectric, using 225 DEG C, 240 DEG C, 255 DEG C of three sections of pre-oxidation furnaces processing, temperature gradient is 15 DEG C, oxygen
Changing circulated air wind speed in furnace is 6m/s, and residence time 80min, draw ratio 0%, obtaining density is 1.35g/cm3Pre-oxidation
Fiber carries out low-temperature carbonization 3min by pre-oxidized fibers under the protection of nitrogen at a temperature of 300~900 DEG C, apply+1% drawing-off
Than；Apply -4% draw ratio at a temperature of 1000~1500 DEG C, high temperature cabonization 3min obtains large-tow carbon fiber.By the carbon of preparation
Fiber epoxy resin E44/ acetone/triethylene tetramine（10:15:1）Liquid gluing is cured as strip, further according to national standard GB/
T3362-2005 carries out Mechanics Performance Testing to corresponding carbon fiber samples, the results are shown in Table 1.
Embodiment 2：
The 24KPAN copolymer fibre produced using Tuozhan Fiber Co., Ltd., Weihai, using 230 DEG C, 243 DEG C, 256 DEG C three
Section pre-oxidation furnace processing, temperature gradient are 13 DEG C, and circulated air wind speed is 7m/s, residence time 65min, draw ratio in oxidation furnace
It is 1%, obtaining density is 1.36g/cm3Pre-oxidized fibers, other technological parameters and operation with embodiment 1, obtain big tow carbon
Fiber the results are shown in Table 1.
Embodiment 3：
The 24KPAN copolymer fibre produced using Tuozhan Fiber Co., Ltd., Weihai, using 220 DEG C, 237 DEG C, 254 DEG C three
Section pre-oxidation furnace processing, temperature gradient are 17 DEG C, and circulated air wind speed is 4m/s, residence time 75min, draw ratio in oxidation furnace
It is 0%, obtaining density is 1.34g/cm3Pre-oxidized fibers, other technological parameters and operation with embodiment 1, obtain big tow carbon
Fiber the results are shown in Table 1.
Comparative example 1：
The 24KPAN copolymer fibre produced using Tuozhan Fiber Co., Ltd., Weihai, using 230 DEG C, 241 DEG C, 252 DEG C three
Section pre-oxidation furnace processing, temperature gradient are 11 DEG C, and circulated air wind speed is 6m/s, residence time 80min, draw ratio in oxidation furnace
It is 1%, obtaining density is 1.35g/cm3Pre-oxidized fibers, other technological parameters and operation with embodiment 1, obtain big tow carbon
Fiber the results are shown in Table 1.
Comparative example 2：
The 24KPAN copolymer fibre produced using Tuozhan Fiber Co., Ltd., Weihai, using 218 DEG C, 237 DEG C, 256 DEG C three
Section pre-oxidation furnace processing, temperature gradient are 19 DEG C, and circulated air wind speed is 5m/s, residence time 70min, draw ratio in oxidation furnace
It is 0.5%, obtaining density is 1.35g/cm3Pre-oxidized fibers, other technological parameters and operation with embodiment 1, obtain big tow
Carbon fiber the results are shown in Table 1.
Comparative example 3：
The 24KPAN copolymer fibre produced using Tuozhan Fiber Co., Ltd., Weihai, using 220 DEG C, 235 DEG C, 250 DEG C three
Section pre-oxidation furnace processing, temperature gradient are 15 DEG C, and circulated air wind speed is 5m/s, residence time 70min, draw ratio in oxidation furnace
It is 0%, obtaining density is 1.32g/cm3Pre-oxidized fibers, other technological parameters and operation with embodiment 1, obtain big tow carbon
Fiber the results are shown in Table 1.
Comparative example 4：
The 24KPAN copolymer fibre produced using Tuozhan Fiber Co., Ltd., Weihai, using 230 DEG C, 245 DEG C, 260 DEG C three
Section pre-oxidation furnace processing, temperature gradient are 15 DEG C, and circulated air wind speed is 6m/s, residence time 80min, draw ratio in oxidation furnace
It is 1%, obtaining density is 1.38g/cm3Pre-oxidized fibers, other technological parameters and operation with embodiment 1, obtain big tow carbon
Fiber the results are shown in Table 1.
Comparative example 5：
The 24KPAN copolymer fibre produced using Tuozhan Fiber Co., Ltd., Weihai, using 228 DEG C, 243 DEG C, 258 DEG C three
Section pre-oxidation furnace processing, temperature gradient are 15 DEG C, and circulated air wind speed is 2m/s, residence time 90min, draw ratio in oxidation furnace
It is 0%, obtaining density is 1.35g/cm3Pre-oxidized fibers, other technological parameters and operation with embodiment 1, obtain big tow carbon
Fiber the results are shown in Table 1.
Comparative example 6：
The 24KPAN copolymer fibre produced using Tuozhan Fiber Co., Ltd., Weihai, using 224 DEG C, 239 DEG C, 254 DEG C three
Section pre-oxidation furnace processing, temperature gradient are 15 DEG C, and circulated air wind speed is 10m/s, residence time 70min, drawing-off in oxidation furnace
Than being 0.5%, obtaining density is 1.35g/cm3Pre-oxidized fibers, other technological parameters and operation with embodiment 1, obtain big silk
Beam carbon fiber, the results are shown in Table 1.
The mechanical performance data of 1. carbon fiber of table
It can be seen that according to the embodiment and comparative example in table 1：
It can be seen that from embodiment 1-3 and comparative example 1,2 corresponding tensile strengths when oxidation furnace recycles wind speed and oxidization fiber
Density, when the temperature gradient of preoxidation process is too small or too big, is easy to cause fibre structure not perfect in control range,
Causing the tensile strength of carbon filament reduces.
It can be seen that from embodiment 1-3 and comparative example 3,4 corresponding tensile strengths when oxidation furnace recycles wind speed and temperature ladder
Degree is in control range, and when oxidization fiber density is too small or too big, defect, the drawing of corresponding carbon filament can be introduced on fibre structure
Stretch strength reduction.
It can be seen that from embodiment 1-3 and comparative example 5,6 corresponding tensile strengths when oxidation furnace temperature gradient and oxidization fiber
Density, when the wind speed of oxidation furnace circulating fan is too small, is unfavorable for homogenizing for pre-oxidized fibers, in fiber in control range
Defect is introduced in structure, the tensile strength of corresponding carbon filament reduces；When the wind speed of oxidation furnace circulating fan is too big, fiber is caused to go out
Existing " share split " phenomenon, is unfavorable for fiber operation stability, leads to the generation of defect, and the tensile strength of corresponding carbon filament also reduces.
It can be seen that from embodiment 1-3 and the corresponding tensile strength of comparative example 1-6 when oxidation furnace circulation wind speed is 4~8m/
S, pre-oxidized fibers density are 1.35 ± 0.02g/cm3, when the pre-oxidation temperature difference is 15 ± 2 DEG C, the tensile strength of gained carbon fiber
It is higher, can be to 4.5Gpa or more, stretch modulus is in 240GPa or so.
Claims (2)
1. a kind of method for pre-oxidizing for preparing large-tow carbon fiber, includes the following steps：By big tow polyacrylonitrile copolymer fibre
It is pre-oxidized in air atmosphere in 180~280 DEG C of temperature ranges, is heat-treated 60~90min using 3 sections of gradient increased temperature modes,
Temperature gradient is 15 ± 2 DEG C, and oxidation furnace circulated air blast velocity control is in 6 ± 2m/s, and under -2~2% draw ratio, obtained density is
1.35±0.02g/cm3Pre-oxidized fibers；Using conventional silicon carbide condition：Under nitrogen protection, under -2~2% draw ratio,
3 ± 1.5min of low-temperature carbonization at 300~900 DEG C, by gained fiber at 1000~1500 DEG C 3 ± 1.5min of high temperature cabonization,
Draw ratio is -5~0%；The big tow polyacrylonitrile copolymer fibre 24K.
2. preparing the method for pre-oxidizing of large-tow carbon fiber according to claim 1, it is characterised in that the big tow is poly-
Acrylonitrile compolymer fiber further includes the copolymer of one or more following monomers in addition to containing acrylonitrile monemer：Itaconic acid, propylene
Acid, methacrylic acid, methyl methacrylate, methyl acrylate.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108396548A (en) * | 2017-02-04 | 2018-08-14 | 中国科学院上海应用物理研究所 | A kind of big tow PAN-based stabilized fiber, large-tow carbon fiber and preparation method thereof |
| CN107287699B (en) * | 2017-07-07 | 2020-08-21 | 中复神鹰碳纤维有限责任公司 | Rapid preoxidation process for polyacrylonitrile-based carbon fiber precursor |
| CN109280998A (en) * | 2018-09-28 | 2019-01-29 | 威海拓展纤维有限公司 | A kind of preparation method of PAN base high-strength and high-modulus type carbon fiber |
| CN110055624B (en) * | 2019-05-20 | 2021-03-09 | 中国科学院山西煤炭化学研究所 | Pre-oxidation method of polyacrylonitrile fiber, polyacrylonitrile carbon fiber and preparation method |
| CN112708970B (en) * | 2019-10-24 | 2022-10-11 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile pre-oxidized fiber |
| CN111074383B (en) * | 2019-12-26 | 2022-06-07 | 长春工业大学 | Preparation method of pre-oxidized fibers for on-line connection of large tow precursors |
| CN111118671B (en) * | 2019-12-26 | 2022-07-12 | 长春工业大学 | Preparation method of 25k large-tow carbon fiber |
| CN111020750B (en) * | 2019-12-26 | 2022-06-07 | 长春工业大学 | High-speed preparation method for producing large-tow carbon fibers |
| CN111647973A (en) * | 2020-07-07 | 2020-09-11 | 北京化工大学常州先进材料研究院 | Preparation method of large-tow carbon fiber |
| CN114941187B (en) * | 2022-06-28 | 2023-04-11 | 中复神鹰碳纤维股份有限公司 | Preparation method of high-performance low-cost carbon fiber |
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| CN102154740A (en) * | 2011-05-13 | 2011-08-17 | 北京化工大学 | Method for preparing high-strength carbon fiber |
| CN103215692A (en) * | 2013-03-26 | 2013-07-24 | 北京化工大学 | Preparation method of high-carbon-yield polyacrylonitrile-based carbon fiber |
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