CN104818546B - The preparation method of high strength and modulus graphite fibre - Google Patents
The preparation method of high strength and modulus graphite fibre Download PDFInfo
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Abstract
The present invention relates to organic polymer field, specifically a kind of preparation method of high strength and modulus graphite fibre, it is characterised in that comprise the following steps：Polyacrylonitrile copolymer fibre is applied into 2~3 times of drawing-off in the steam drafting stage, precursor of the degree of orientation 91~93% is obtained；By obtained precursor 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；By gained pre-oxidized fibers 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 3 ± 1.5min of high temperature cabonization; draw ratio is 4~0%, obtains phosphorus content more than 96%, a diameter of 7 μm of carbon fiber；By gained carbon fiber under inert gas shielding, in 2 ± 1min of graphitization at 2200~2500 DEG C, draw ratio is 1~5%, obtains graphite fibre.
Description
Technical field
The present invention relates to Carbon Fiber Technology field, specifically a kind of preparation side of high strength and modulus graphite fibre
Method.
Background technology
It is known that polyacrylonitrile-radical（PAN）The preparation process of graphite fibre mainly include precursor shaping, pre-oxidation, it is low
The stages such as temperature carbonization, high temperature cabonization and graphitization.Size, distribution, defect level and orientation of graphite microcrystal etc. are determined
Its performance, and the structure of graphite fibre depends on the structurally consummate degree of carbon fiber, therefore, it can by controlling precursor and pre- oxygen
Structurally consummate carbon fiber is made in the structure of chemical fibre dimension, so as to obtain structurally consummate and graphite fibre of excellent performance.
Precursor fine-denierization has turned into one of Major Technology of raising precursor intensity and production high-performance carbon fibre, in order to
High-intensity fine denier precursor is prepared, steam drafting need to be carried out to PAN fiber tow under some tension, that is, ensure fibre strength
Under conditions of, drafting multiple is suitably adjusted according to the requirement of fiber fine-denier, general steam drafting multiple is between 2~3.Drawing-off
Multiple is less than 2, it is impossible to ensure that the intensity of fiber reaches requirement, and the excessive phenomenon of drawing-off is then easily produced higher than 3 times.Steam drafting
Changed the morphosis of fiber, in the presence of drafting stress and fuel factor, the mobility of macromolecular chain segment increases
Plus, various construction units are uprised along fiber axially aggregation, rearrangement, molecular chain orientation degree, and strand is stretched, and makes fiber
In more strands be in optimum stress state.Therefore, with the increase of drafting multiple, the rise of precursor degree of orientation, fiber
Intensity improve.
In preoxidation process, control oxidization fiber density is conventional effective method.Oxygen content control in oxidization fiber
System is 8~10%, and its density should be controlled in 1.32~1.36g/cm3Between.When oxidization fiber density is less than 1.32g/cm3When, pre- oxygen
Change is insufficient, and pre-oxidized fibers easily occur to melt simultaneously in carbonation stage, introduce defect in PAN macromolecular chains, cause carbon fiber
Can reduction.When oxidization fiber density is higher than 1.36g/cm3When, pre-oxidation is excessive, and the oxygen element combined on PAN strands is excessive,
Oxygen is with H in carbonisation2O、CO、CO2Small molecule form runaway, introduce defect on PAN strands, cause carbon fiber close
Degree declines and performance reduction.
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 preparation of high strength and modulus graphite fibre
Method, drafting multiple of the control fiber in the steam drafting stage obtains the higher precursor of the degree of orientation, control precursor is in pre-oxidation rank
The technological parameter of section, obtains structurally consummate pre-oxidized fibers, controls the temperature and tension force in high temperature cabonization stage, obtains phosphorus content
Carbon fiber more than 96%, so that high strength and modulus graphite fibre is made.
The present invention solve above-mentioned technical problem use technical scheme be：A kind of preparation of high strength and modulus graphite fibre
Method, it is characterised in that comprise the following steps：Polyacrylonitrile copolymer fibre is applied into 2~3 times in the steam drafting stage to lead
Stretch, obtain precursor of the degree of orientation 91~93%.By obtained precursor in air atmosphere in pre- in 180~280 DEG C of temperature ranges
Oxidation, 60~110min is heat-treated using 6 sections of gradient increased temperature modes, and it is 1.34 ± 0.02g/cm that density, which is made,3Pre-oxidation it is fine
Dimension.By gained pre-oxidized fibers under nitrogen protection, under 0~4% draw ratio, in low-temperature carbonization 3 at 300~900 DEG C ±
1.5min, by gained fiber at 1000~1800 DEG C 3 ± 1.5min of high temperature cabonization, draw ratio be -4~0%, obtain phosphorus content
More than 96%, a diameter of 7 μm of carbon fiber.By gained carbon fiber under inert gas shielding, in graphitization at 2200~2500 DEG C
2 ± 1min, draw ratio is 1~5%, obtains graphite fibre.
Above-mentioned polyacrylonitrile copolymer fibre beam can be divided into 1~48K.Above-mentioned polyacrylonitrile copolymer fibre is except containing propylene
Outside nitrile monomer, include the copolymer of one or more following monomers：Itaconic acid, acrylic acid, methacrylic acid, methacrylic acid
Methyl esters, methyl acrylate, hydroxyalkyl acrylonitrile, hydroxyalkyl acrylic acid and its esters, acrylamide, methylene succinic acid, methyl-prop
Acrylamide, methacrylaldehyde, MAL, allyl chloride, α-chloropropene, diacetone acrylamide, metering system benzylacetone, second
Vinyl pyrrolidone.
The beneficial effects of the invention are as follows carry out mechanical property sign to prepared graphite fibre tow, as a result show：Take
It is 91~93% precursor to degree, it is 1.34 ± 0.02g/cm that density, which is made, by pre-oxidation3Pre-oxidized fibers, then through too high
Phosphorus content is made more than 96% in temperature carbonization, a diameter of 7 μm of carbon fiber, and graphitization is carried out at 2200~2500 DEG C and is stretched
Intensity is higher than 4.5GPa, and stretch modulus is higher than 390 GPa graphite fibre.Proved by example, the degree of orientation of precursor, pre-oxidation
The size of fibre density and carbon fiber phosphorus content will influence the structure and performance of graphite fibre, can be by controlling precursor
The phosphorus content of the degree of orientation, the density of pre-oxidized fibers and carbon fiber improves the structure of graphite fibre and improves its mechanical property
Can, there is good directive significance to preparing high strength and modulus graphite fibre.
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）=
96：2：2）, in 2.1 times of drawing-off of steam drafting stage application, the precursor that the degree of orientation is 91.5% is made, precursor is situated between in air
In matter, using 190 DEG C, 210 DEG C, 225 DEG C, 235 DEG C, 245 DEG C, 265 DEG C of six sections of pre-oxidation treatments, the residence time is 90min, is led
Stretch than for 1%, obtaining density for 1.34g/cm3Pre-oxidized fibers, by pre-oxidized fibers under the protection of nitrogen, 300~900
Low-temperature carbonization is carried out at a temperature of DEG C, the residence time is 3min, apply+2% draw ratio；Apply -3% at a temperature of 1000~1800 DEG C
Draw ratio, high temperature cabonization 3min, it is 97.0% that phosphorus content, which is made, and a diameter of 7 μm of carbon fiber carries out stone at a temperature of 2400 DEG C
Mo Hua, the residence time is 2.5min, applies+2% draw ratio, obtains graphite fibre.By the graphite fibre epoxy resin of preparation
E44/ acetone/triethylene tetramine（10：15：1）Liquid gluing is cured as strip, further according to national standard GB/T 3362-2005 to corresponding
Carbon fiber samples carry out Mechanics Performance Testing, the results are shown in Table 1.
Embodiment 2：
The 12K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai, 2.3 times are applied in the steam drafting stage
Drawing-off, be made the degree of orientation be 92.2% precursor, other technological parameters and operation be the same as Example 1, obtain graphite fibre, as a result
It is shown in Table 1.
Embodiment 3：
The 12K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai, 2.5 times are applied in the steam drafting stage
Drawing-off, be made the degree of orientation be 92.8% precursor, other technological parameters and operation be the same as Example 1, obtain graphite fibre, as a result
It is shown in Table 1.
Embodiment 4：
The 12K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai, by precursor in air dielectric, are used
190 DEG C, 205 DEG C, 220 DEG C, 233 DEG C, 245 DEG C, 260 DEG C of six sections of pre-oxidation treatments, the residence time is 100min, and draw ratio is
1.5%, density is obtained for 1.33g/cm3Pre-oxidized fibers, other technological parameters and operation be the same as Example 2 obtain graphite fine
Dimension, the results are shown in Table 1.
Embodiment 5：
The 12K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai, by precursor in air dielectric, are used
190 DEG C, 210 DEG C, 230 DEG C, 245 DEG C, 255 DEG C, 270 DEG C of six sections of pre-oxidation treatments, the residence time is 85min, and draw ratio is
0.5%, density is obtained for 1.35g/cm3Pre-oxidized fibers, other technological parameters and operation be the same as Example 2 obtain graphite fine
Dimension, the results are shown in Table 1.
Embodiment 6：
The 3K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai（Copolymer composition is identical with 12K）, its
Its technological parameter and operation be the same as Example 1, obtain graphite fibre, the results are shown in Table 1.
Embodiment 7：
The 3K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai（Copolymer composition is identical with 12K）, its
Its technological parameter and operation be the same as Example 2, obtain graphite fibre, the results are shown in Table 1.
Embodiment 8：
The 3K PAN copolymer fibres produced using Tuozhan Fiber Co., Ltd., Weihai（Copolymer composition is identical with 12K）, its
Its technological parameter and operation be the same as Example 3, obtain graphite fibre, the results are shown in Table 1.
The mechanical performance data of the graphite fibre of table 1
It can be drawn according in the embodiment of table 1 correspondence graphite fibre mechanical performance data to draw a conclusion：
It is can be seen that from the tensile strength and stretch modulus of the correspondence graphite fibre of embodiment 1~3 and 6~8 when oxidization fiber is close
Spend for 1.34g/cm3When, with the increase of the precursor degree of orientation, the tensile strength and stretch modulus of gained graphite fibre gradually increase.
It is can be seen that from the tensile strength and stretch modulus of the correspondence graphite fibre of embodiment 2,4 and 5 when the precursor degree of orientation is
When 92.2%, with the increase of oxidization fiber density, the tensile strength and stretch modulus first increases and then decreases of gained graphite fibre；When pre-
Oxygen silk density is 1.34g/cm3When, the tensile strength and stretch modulus highest of gained graphite fibre.
It is can be seen that from the tensile strength and stretch modulus of the correspondence graphite fibre of embodiment 1~8 when the precursor degree of orientation is 91
~93%, oxidization fiber density is 1.34 ± 0.02g/cm3When, the performance of gained graphite fibre is higher, and tensile strength reaches 4.5
More than Gpa, stretch modulus reaches more than 390GPa.
Claims (3)
1. a kind of preparation method of high strength and modulus graphite fibre, it is characterised in that comprise the following steps：Polyacrylonitrile is total to
Poly- fiber applies 2~3 times of drawing-off in the steam drafting stage, obtains precursor of the degree of orientation 91~93%；Obtained precursor is existed
In being pre-oxidized in 180~280 DEG C of temperature ranges under air atmosphere, 60~110min is heat-treated using 6 sections of gradient increased temperature modes, is made
It is 1.34 ± 0.02g/cm to obtain density3Pre-oxidized fibers；By gained pre-oxidized fibers under nitrogen protection, led 0~4%
Stretch than under, in 3 ± 1.5min of low-temperature carbonization at 300~900 DEG C, by gained fiber at 1000~1800 DEG C high temperature cabonization 3 ±
1.5min, draw ratio is -4~0%, obtains phosphorus content more than 96%, a diameter of 7 μm of carbon fiber；By gained carbon fiber in inertia
Under gas shield, in 2 ± 1min of graphitization at 2200~2500 DEG C, draw ratio is 1~5%, obtains graphite fibre.
2. the preparation method of high strength and modulus graphite fibre according to claim 1, it is characterised in that described polypropylene
Nitrile copolymer fibre beam can be divided into 1~48K.
3. the preparation method of high strength and modulus graphite fibre according to claim 1, it is characterised in that described polypropylene
Nitrile copolymer fibre is in addition to containing acrylonitrile monemer, to include the copolymer of one or more following monomers：Itaconic acid, acrylic acid,
Methacrylic acid, methyl methacrylate, methyl acrylate, hydroxyalkyl acrylonitrile, hydroxyalkyl acrylic acid and its esters, acryloyl
Amine, methylene succinic acid, Methacrylamide, methacrylaldehyde, MAL, allyl chloride, α-chloropropene, two acetone acryloyls
Amine, metering system benzylacetone, vinyl pyrrolidone.
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| 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 |
| CN108193324A (en) * | 2017-12-26 | 2018-06-22 | 宜兴市天宇世纪高新科技有限公司 | A kind of production technology of polyacrylonitrile-based carbon fibre |
| CN109989127A (en) * | 2017-12-31 | 2019-07-09 | 福建恒安集团有限公司 | A kind of hot-wind nonwoven cloth material |
| CN109252250B (en) * | 2018-08-06 | 2019-10-15 | 威海拓展纤维有限公司 | The carbonization treatment method of polyacrylonitrile-based carbon fibre |
| CN109402790A (en) * | 2018-09-20 | 2019-03-01 | 北京化工大学 | High-orientation polyacrylonitrile fibril and its preparation method and application for obtaining high-strength high-modules carbon fibre |
| CN109280997A (en) * | 2018-09-20 | 2019-01-29 | 北京化工大学 | The high-strength high-modules carbon fibre and preparation method thereof of low degree of graphitization |
| 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 |
| CN109468712B (en) * | 2018-10-24 | 2021-02-09 | 北京化工大学 | High-modulus carbon fiber and method for preparing high-modulus carbon fiber by regulating and controlling thermal stabilization fiber oxygen ring structure |
| CN110409018A (en) * | 2019-08-08 | 2019-11-05 | 中复神鹰碳纤维有限责任公司 | The preparation method of dry-jet wet-spinning high-strength and high-modulus wear-resisting polypropene itrile group carbon fiber |
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| TWI527946B (en) * | 2012-04-12 | 2016-04-01 | 三菱麗陽股份有限公司 | Carbon fiber precursor acrylic fiber bundle and method for producing the same, thermal oxide treatment furnace and method for producing carbon fiber |
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