CN104651979B - The method for preparing high-strength middle model carbon fiber - Google Patents
The method for preparing high-strength middle model carbon fiber Download PDFInfo
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- CN104651979B CN104651979B CN201510117206.7A CN201510117206A CN104651979B CN 104651979 B CN104651979 B CN 104651979B CN 201510117206 A CN201510117206 A CN 201510117206A CN 104651979 B CN104651979 B CN 104651979B
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Abstract
The present invention relates to organic polymer field, specifically a kind of method for preparing high-strength middle model carbon fiber comprises the following steps：By polyacrylonitrile copolymer fibre tow in air atmosphere in being pre-oxidized in 180~280 DEG C of temperature ranges, 60~110min is heat-treated using 6 sections of gradient increased temperature modes, it is 1.34 ± 0.02g/cm that density, which is made,3Pre-oxidized fibers, then by conventional silicon carbide condition：Nitrogen protection under, under 0~4% draw ratio, in 3 ± 1.5min of low-temperature carbonization at 300~900 DEG C, by gained fiber at 1000~1800 DEG C 3 ± 1.5min of high temperature cabonization, draw ratio be 4~0%；Wherein, it is necessary to control low temperature oven pipeline pressure between 5~15Pa during low-temperature carbonization.Size of the present invention in low-temperature carbonization stage control pipeline pressure, the structure and performance of pre- carbon fibre and carbon fiber will be influenceed, the structure of carbon fiber can be improved by controlling the pressure of low-temperature carbonization stage pipeline and its mechanical property is improved, so as to prepare high-strength middle model carbon fiber.
Description
Technical field
The present invention relates to Carbon Fiber Technology field, specifically a kind of method for preparing high-strength middle model carbon fiber.
Background technology
It is known that polyacrylonitrile-radical（PAN）The preparation process of carbon fiber mainly includes precursor shaping, pre-oxidation, low temperature
The stage such as carbonization and high temperature cabonization.During low-temperature carbonization, fiber can discharge substantial amounts of waste gas（CO、CO2、NH3、CH4、H2O
Deng）And tar.Tar once stains fiber, is gently then hardened, embrittlement, heavy then fracture of wire.Do not allow waste gas be condensed into stove tar and
Instantaneous discharge waste gas, tar are one of stabilised quality, the key factor of steady production.At present, for PAN pre-oxidized fibers low temperature
The research of carbonization, is confined to how to make the pyrolysis off-gas in low temperature carbonization furnace not to be condensed into tar and instantaneously discharge out of the furnace.However,
With CO, CO2、NH3、CH4、H2The release of the gases such as O, complicated chemical change occurs in fiber, from heat-resisting trapezium structure to unrest
The conversion of layer graphite-structure.According to document introduction, the heat chemistry in the stage changes the shadow of main heat-treated temperature, time and tension force
Ring.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of side for preparing high-strength middle model carbon fiber
Method, by rationally controlling the pipeline pressure of low-temperature carbonization stage, carrys out the perfect pre- carbon fibre of preparation structure, so as to be made high-strength
Middle model carbon fiber.
The present invention solve above-mentioned technical problem use technical scheme be：A kind of side for preparing high-strength middle model carbon fiber
Method, comprises the following steps：
By polyacrylonitrile copolymer fibre tow in air atmosphere in being pre-oxidized in 180~280 DEG C of temperature ranges, using 6
Section gradient increased temperature mode is heat-treated 60~110min, and it is 1.34 ± 0.02g/cm that density, which is made,3Pre-oxidized fibers, then by normal
Advise Carbonization Conditions：Under nitrogen protection, under 0~4% draw ratio, in 3 ± 1.5min of low-temperature carbonization at 300~900 DEG C, by institute
Fiber 3 ± 1.5min of high temperature cabonization at 1000~1800 DEG C is obtained, draw ratio is -4~0%；Wherein, during low-temperature carbonization,
Control low temperature oven pipeline pressure is needed between -5~-15Pa.
The fiber that above-mentioned polyacrylonitrile copolymer fibre tow can be spinned using wet method or wet-dry change.Polyacrylonitrile copolymerization is fine
Dimension tow is 1~48K.Above-mentioned polyacrylonitrile copolymer fibre silk be in addition to containing acrylonitrile monemer, in addition to one or more with
The copolymer of lower monomer：Itaconic acid, acrylic acid, methacrylic acid, methyl methacrylate, methyl acrylate, hydroxyalkyl propylene
Nitrile, hydroxyalkyl acrylic acid and its esters, acrylamide, methylene succinic acid, Methacrylamide, methacrylaldehyde, MAL, alkene
Propyl chloride, α-chloropropene, diacetone acrylamide, metering system benzylacetone, vinyl pyrrolidone.
The beneficial effects of the invention are as follows in the size of low-temperature carbonization stage control pipeline pressure, it will the pre- carbonization of influence is fine
The structure and performance of dimension and carbon fiber, can improve the structure of carbon fiber by controlling the pressure of low-temperature carbonization stage pipeline
With improve its mechanical property, so as to prepare high-strength middle model carbon fiber.
Embodiment
With reference to embodiment, the invention will be further described：
Embodiment 1：
What the Tuozhan Fiber Co., Ltd., Weihai for selecting wet method to spin produced, the PAN containing more than 90% acrylonitrile monemer component is total to
Poly- fiber（Its tow is 12K, copolymer composition（wt%）For：Acrylonitrile（AN）:Methyl acrylate（MA）:Itaconic acid（IA）=
96:2.0:2.0）, in air dielectric, using 190 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 260 DEG C of six sections of pre-oxidation furnaces
Processing, the residence time is 90min, and draw ratio is 1%, obtains density for 1.34g/cm3Pre-oxidized fibers, by pre-oxidized fibers
Under the protection of nitrogen, low-temperature carbonization is carried out at a temperature of 300~900 DEG C, the residence time is 3min, apply+3% draw ratio；
The draw ratio of application -3%, high temperature cabonization 3min at a temperature of 1000~1800 DEG C.Wherein, during low-temperature carbonization, low temperature is controlled
Stove pipeline pressure is -6Pa, obtains carbon fiber.By the carbon fiber of preparation epoxy resin E44/ acetone/triethylene tetramine（10:
15:1）Liquid gluing is cured as strip, and mechanical property is carried out to corresponding carbon fiber samples further according to national standard GB/T 3362-2005
It can test, the results are shown in Table 1.
Embodiment 2：
The 12K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai, during low-temperature carbonization, are controlled low
Warm stove pipeline pressure is -9Pa, other technological parameters and operation be the same as Example 1, obtains carbon fiber, the results are shown in Table 1.
Embodiment 3：
The 12K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai, during low-temperature carbonization, are controlled low
Warm stove pipeline pressure is -12Pa, other technological parameters and operation be the same as Example 1, obtains carbon fiber, the results are shown in Table 1.
Embodiment 4：
The 12K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai, during low-temperature carbonization, are controlled low
Warm stove pipeline pressure is -15Pa, other technological parameters and operation be the same as Example 1, obtains carbon fiber, the results are shown in Table 1.
Comparative example 1：
The 12K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai, during low-temperature carbonization, are controlled low
Warm stove pipeline pressure is -1Pa, other technological parameters and operation be the same as Example 1, obtains carbon fiber, the results are shown in Table 1.
Comparative example 2：
The 12K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai, during low-temperature carbonization, are controlled low
Warm stove pipeline pressure is -3Pa, other technological parameters and operation be the same as Example 1, obtains carbon fiber, the results are shown in Table 1.
Comparative example 3：
The 12K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai, during low-temperature carbonization, are controlled low
Warm stove pipeline pressure is -20Pa, other technological parameters and operation be the same as Example 1, obtains carbon fiber, the results are shown in Table 1.
Comparative example 4：
The 12K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai, during low-temperature carbonization, are controlled low
Warm stove pipeline pressure is -25Pa, other technological parameters and operation be the same as Example 1, obtains carbon fiber, the results are shown in Table 1.
The mechanical performance data of the carbon fiber of table 1.
Embodiment and comparative example in table 1 can be seen that：
It can be seen that when LT stove pipeline pressures are relatively low, no from comparative example 1-2 and the corresponding tensile strengths of embodiment 1-4
Beneficial to the perfect of carbon fiber structural.
It is can be seen that from embodiment 1-4 and the corresponding tensile strengths of comparative example 3-4 and stretch modulus when LT stove pipeline pressures
When excessive, defect is easily introduced on fibre structure.
LT stove pipeline pressures are can be seen that from embodiment 1-4 and the corresponding tensile strengths of comparative example 1-4 and stretch modulus
During for -10 ± 5Pa, the tensile strength of gained carbon fiber is higher, can be to more than 5.5Gpa, and stretch modulus is in more than 290GPa.
Test sample preparation method of the present invention：By the carbon fiber epoxy resin, solvent and curing agent mixing liquid of preparation
Gluing is cured as after strip, and the preparation of sample is carried out with epoxy resin and curing agent, after sample is prepared, and fibre bundle is carried out
Mechanics Performance Testing.
The present invention carries out mechanical property sign to prepared carbon fibre tow, as a result shows：Density be 1.34 ±
0.02g/cm3Pre-oxidized fibers, in 300~900 DEG C of heat treatment process, when the stage pipeline pressure be -10 ± 5Pa
When, the tensile strength of gained carbon fiber is higher than 5.5GPa, and modulus is higher than 290 GPa.Proved by example, in low-temperature carbonization stage
The size of control pipeline pressure, it will the structure and performance of the pre- carbon fibre of influence and carbon fiber, can be by controlling low temperature
The pressure of carbonation stage pipeline come improve carbon fiber structure and improve its mechanical property, have to preparing high-strength middle model carbon fiber
Good directive significance.
The present invention proposes a kind of new process control parameter：Pipeline pressure；When pressure is smaller, it is unfavorable for the row of tar
Put, easily pollute fiber；When pressure is excessive, the air-proof condition requirement on the one hand to low temperature oven is strict, on the other hand, causes stove
Interior negative pressure value is excessive, under identical heat treatment temperature, it is easier to cause the release of micro-molecular gas, in fiber on strand
Defect is introduced, is unfavorable for the perfect of carbon fiber structural.So answering the pipeline pressure in the reasonable set stage, to carry out preparation structure perfect
Pre-oxidized fibers, so as to prepare high-strength middle model carbon fiber.
Claims (4)
1. a kind of method for preparing high-strength middle model carbon fiber, it is characterised in that comprise the following steps：Polyacrylonitrile copolymerization is fine
Tow is tieed up in air atmosphere in being pre-oxidized in 180~280 DEG C of temperature ranges, 60 are heat-treated using 6 sections of gradient increased temperature modes~
110min, it is 1.34 ± 0.02g/cm that density, which is made,3Pre-oxidized fibers, then by conventional silicon carbide condition：Under nitrogen protection,
Under 0~4% draw ratio, in 3 ± 1.5min of low-temperature carbonization at 300~900 DEG C, by gained fiber at 1000~1800 DEG C it is high
Temperature 3 ± 1.5min of carbonization, draw ratio is -4~0%；Wherein, it is necessary to control low temperature oven pipeline pressure during low-temperature carbonization
Between -5~-15Pa.
2. the method for high-strength middle model carbon fiber is prepared according to power requires 1, it is characterised in that described polyacrylonitrile copolymerization
The fiber that fibre bundle can be spinned using wet method or wet-dry change.
3. the method for high-strength middle model carbon fiber is prepared according to power requires 1, it is characterised in that described polyacrylonitrile copolymerization
Fibre bundle is 1~48K.
4. the method for high-strength middle model carbon fiber is prepared according to power requires 1, it is characterised in that described polyacrylonitrile copolymerization
Filament is in addition to containing acrylonitrile monemer, to include the copolymer of one or more following monomers：Itaconic acid, acrylic acid, methyl
Acrylic acid, methyl methacrylate, methyl acrylate, hydroxyalkyl acrylonitrile, hydroxyalkyl acrylic acid and its esters, acrylamide,
Methylene succinic acid, Methacrylamide, methacrylaldehyde, MAL, allyl chloride, α-chloropropene, diacetone acrylamide,
Metering system benzylacetone, vinyl pyrrolidone.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106567158A (en) * | 2016-11-11 | 2017-04-19 | 宁波艾盛环保科技有限公司 | Preparation method of bioactive carbon fiber |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106592019B (en) * | 2015-10-19 | 2019-04-12 | 中国石油化工股份有限公司 | The preparation method of polyacrylonitrile-radical high-performance carbon fibre |
| CN105401262A (en) * | 2015-12-21 | 2016-03-16 | 中复神鹰碳纤维有限责任公司 | Middle-modulus carbon fiber preparation method based on rapid spinning and high denier precursor |
| CN107653520A (en) * | 2017-10-20 | 2018-02-02 | 东华大学 | A kind of preparation method of cost degradation polyacrylonitrile-based carbon fibre |
| CN108221075A (en) * | 2018-02-06 | 2018-06-29 | 威海拓展纤维有限公司 | A kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance |
| CN111088557A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Method for preparing high-performance carbon fiber by controlling polyacrylonitrile thermal stabilization fiber structure |
| 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 |
| CN111118671B (en) * | 2019-12-26 | 2022-07-12 | 长春工业大学 | Preparation method of 25k large-tow carbon fiber |
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