CN110331470A - Band shape polyacrylonitrile carbon fiber and preparation method thereof - Google Patents
Band shape polyacrylonitrile carbon fiber and preparation method thereof Download PDFInfo
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- CN110331470A CN110331470A CN201910731644.0A CN201910731644A CN110331470A CN 110331470 A CN110331470 A CN 110331470A CN 201910731644 A CN201910731644 A CN 201910731644A CN 110331470 A CN110331470 A CN 110331470A
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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
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
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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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Abstract
The invention discloses a kind of band shape polyacrylonitrile carbon fibers and preparation method thereof, wherein preparation method includes: (1) by acrylonitrile monemer and itaconic acid, methyl acrylate and solvent progress combined polymerization, to obtain polymer spinning solution；(2) through coagulating bath solidification draw forming be band shape polyacrylonitrile as-spun fibre after the spinneret spinneret with shape spinneret orifice by the polymer spinning solution, the band shape polyacrylonitrile as-spun fibre through a drawing-off, wash, the compacting by drying that oils, secondary drawing-off, band shape polyacrylonitrile fibril be made after thermal finalization；(3) by the band shape polyacrylonitrile fibril through pre-oxidation, low-temperature carbonization and high temperature cabonization, to obtain banding pattern polyacrylonitrile carbon fiber.Compared to typical round section carbon fibre, the band shape polyacrylonitrile carbon fiber long axis obtained using the present invention is up to 22.3~24.2 microns, 5.1~5.4 microns of short axle, fiber number is up to 0.154~0.174tex, and monofilament tensile strength is not less than 5.4GPa, stretch modulus up to 294GPa.
Description
Technical field
The invention belongs to carbon material technical fields, specifically, the present invention relates to a kind of band shape polyacrylonitrile carbon fiber and
Preparation method.
Background technique
High-performance polyacrylonitrile carbon fiber has the excellent properties such as high specific strength, high ratio modulus, high temperature resistant, as composite wood
The reinforcement of material is widely used in the fields such as military affairs, Aeronautics and Astronautics, civilian industry and Leisure Sport.
Polyacrylonitrile carbon fiber is that polyacrylonitrile fibril is obtained through pre-oxidation carbonization, and preoxidation process passes through cyclization, dehydrogenation
It is changed into heat-resisting trapezium structure with oxidation reaction, is amenable to high temperature cabonization process.The oxidation reaction of preoxidation process can accelerate
Cyclization and dehydrogenation reaction, simultaneous oxidation are cross-linked to form the more excellent cross-linked network structure of stability.Oxidation reaction is related to oxygen
For son in fiber radial diffusion, circular cross-section PAN precursor diameter is excessive, and the diffusion path of oxygen increases, and is easy to be formed in pre-oxidation
Skin-core structure difference, to influence the performance of carbon fiber.It is existing studies have shown that when precursor diameter is less than 11 microns, can be with
The pre- oxide structure of homogeneous is formed, carbon fiber tensile strength is up to 5.4GPa；When precursor diameter is greater than 11 microns, it is difficult to eliminate pre-
Oxygen skin-core structure.Thus, the diameter maximum for the carbon fiber product that the outer carbon fiber industry of Current Domestic provides only has 7 microns, this
Diameter carbon fibers tensile strength maximum can only achieve 4.9GPa.However, it is increasing to large-sized carbon fiber demand, using existing
Some technologies hardly result in the large-size carbon fiber haveing excellent performance.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of band shape polyacrylonitrile carbon fiber and preparation method thereof, the party
Then method obtains band shape poly- third through coagulating bath solidification draw forming by using having the spinneret with shape spinneret orifice to carry out spinning
Alkene nitrile as-spun fibre, then through a drawing-off, wash, the compacting by drying that oils, secondary drawing-off, band shape polypropylene be made after thermal finalization
Nitrile precursor, the band shape polyacrylonitrile fibril is in preoxidation process, due to the presence of precursor short axle so that oxygen diffusion path compared with
Short, oxygen element can be easy to be diffused into inside precursor through precursor short axle, obtain the pre- oxide structure of homogeneous, can most make after being carbonized afterwards
It is standby to obtain high-performance carbon fibre, since major axis dimension is larger, it is expected to solve traditional PAN fiber sectional dimension limitation problem.
In one aspect of the invention, the invention proposes a kind of methods prepared with shape polyacrylonitrile carbon fiber.According to
The embodiment of the present invention, which comprises (1) be copolymerized acrylonitrile monemer and itaconic acid, methyl acrylate and solvent
It closes, to obtain polymer spinning solution；(2) by the polymer spinning solution after the spinneret spinneret with shape spinneret orifice
It is band shape polyacrylonitrile as-spun fibre through coagulating bath solidification draw forming, the band shape polyacrylonitrile as-spun fibre is once led
It stretches, wash, the compacting by drying that oils, secondary drawing-off, band shape polyacrylonitrile fibril being made after thermal finalization；(3) the band shape is gathered
Acrylonitrile precursor is through pre-oxidation, low-temperature carbonization and high temperature cabonization, to obtain banding pattern polyacrylonitrile carbon fiber.
Preferably, in step (2), there are multiple band shape spinneret orifices on the spinneret, the long axis of the spinneret orifice is
0.40~0.45mm, short axle are 0.050~0.055mm.
Preferably, in step (2), the temperature of the polymer spinning solution is 50~70 degrees Celsius, the spinneret speed
Degree is 2.25~3.75m/min.
Optional, described be set in three-level coagulating bath carries out, and it is 1.8~3m/min, level-one that level-one, which solidifies draft speed,
Coagulation bath temperature is 35~55 degrees Celsius.
Preferably, in step (2), the long axis with shape polyacrylonitrile as-spun fibre is 390~440 microns, short axle
It is 49~64 microns.
Preferably, in step (2), the draft ratio of a drawing-off is 3~9 times, preferably 4.5~7 times.
Preferably, in step (2), after a drawing-off, the long axis of fiber is 55~85 microns, short axle is 15~
22 microns.
Preferably, in step (2), the draft ratio of the secondary drawing-off is 2~4 times, preferably 2.2~2.8 times.
Preferably, in step (2), after the secondary drawing-off, the long axis of fiber is 30~33 microns, and short axle is
10.6~11.4 microns.
Preferably, in step (2), the fiber number with shape polyacrylonitrile fibril is 0.30~0.36tex.
In another aspect of the invention, the invention proposes a kind of band shape polyacrylonitrile carbon fibers.It is according to the present invention
Embodiment, the band shape polyacrylonitrile carbon fiber is adopted to be prepared with the aforedescribed process.
Preferably, the carbon fiber long axis is 22.3~24.2 microns, and short axle is 5.1~5.4 microns, fiber number 0.154
~0.174tex, monofilament tensile strength are not less than 5.4GPa, stretch modulus 294GPa.
Then the present invention solidifies draw forming through coagulating bath by using having the spinneret with shape spinneret orifice to carry out spinning
Obtain band shape polyacrylonitrile as-spun fibre, then through a drawing-off, wash, the compacting by drying that oils, secondary drawing-off, make after thermal finalization
Band shape polyacrylonitrile fibril is obtained, that is, keeps or slightly reduce precursor minor axis dimension, increases precursor major axis dimension, the band shape polyacrylonitrile
Precursor is in preoxidation process, and due to the presence of precursor short axle, so that oxygen diffusion path is shorter, oxygen molecule can be through precursor short axle very
It readily diffuses into inside precursor, reduces the formation of skin-core structure, obtain the pre- oxide structure of homogeneous, and because shorten oxygen element
Diffusion path improves production efficiency so reducing the time of preoxidation process, production cost is reduced, most afterwards through being carbonized
After high-performance carbon fibre can be prepared, be expected to solve traditional PAN fiber sectional dimension limitation problem.And carbon fiber of the present invention
Tie up short axle size it is suitable with round carbon fiber diameter of section when, band shape carbon fiber of the invention due to bigger long axis, thus
Sectional area is bigger (sectional area compared with circular cross-section carbon fiber increases 4 times), carbon fiber preparation efficiency and composite material preparation effect
Rate will be greatly improved.Compared to typical round section carbon fibre, band shape polyacrylonitrile carbon fiber long axis of the invention is reachable
22.3~24.2 microns, short axle is up to 5.1~5.4 microns, and for fiber number up to 0.154~0.174tex, monofilament tensile strength is not low
In 5.4GPa, stretch modulus up to 294GPa.
Detailed description of the invention
Fig. 1 is method flow schematic diagram of the preparation with shape polyacrylonitrile carbon fiber according to an embodiment of the present invention；
Fig. 2 is the bottom view for the spinneret that the present invention uses；
Fig. 3 is the enlarged drawing of spinneret orifice on the spinneret of the invention used；
Fig. 4 be embodiment 1 obtain with the cross-section photograph under shape polyacrylonitrile fibril optical microscopy；
Fig. 5 A is the band shape polyacrylonitrile carbon fiber section electromicroscopic photograph that embodiment 1 obtains；
Fig. 5 B is the band shape polyacrylonitrile carbon fiber section electromicroscopic photograph that embodiment 2 obtains；
Fig. 5 C is the band shape polyacrylonitrile carbon fiber surface electromicroscopic photograph that embodiment 1 obtains；
Fig. 6 A is the round polyacrylonitrile carbon fiber surface electromicroscopic photograph that comparative example obtains；
Fig. 6 B is the round polyacrylonitrile carbon fiber cross section electromicroscopic photograph that comparative example obtains.
Specific embodiment
Below by conjunction with the embodiments and its Fig. 1-3 the invention will be further described, following embodiment is descriptive
, it is not restrictive, this does not limit the scope of protection of the present invention.
It should be noted that Denier unit tex herein, Tekes, are defined as the quality that fiber filament length is 1000m
(g)。
In one aspect of the invention, the invention proposes a kind of methods prepared with shape polyacrylonitrile carbon fiber.According to
The embodiment of the present invention, with reference to Fig. 1, this method comprises:
S1: acrylonitrile monemer and itaconic acid, methyl acrylate and solvent are subjected to combined polymerization
In the step, acrylonitrile, itaconic acid, methyl acrylate, azodiisobutyronitrile and solvent dimethyl sulfoxide are carried out
Combined polymerization obtains polymer spinning solution.Specifically, during being somebody's turn to do, with dimethyl sulfoxide (DMSO) for solvent, 60~70
DEG C, it is that initiator carries out acrylonitrile, methyl acrylate, itaconic acid three with azo-bis-isobutyl cyanide (AIBN) at a temperature of preferably 65 DEG C
First solution copolymerization reacts 12~36 hours, preferably 24 hours, obtains polymer spinning solution, wherein acrylonitrile, acrylic acid
The mass ratio of methyl esters and itaconic 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, 7~9 hours
It is preferred that stopping stirring after 8 hours, the standing and defoaming under 55~65 DEG C preferably 60 DEG C same vacuum conditions obtains polyacrylonitrile spinning
Silk liquid.
S2: it is through coagulating bath solidification draw forming after the spinneret spinneret with shape spinneret orifice by polymer spinning solution
Band shape polyacrylonitrile as-spun fibre, band shape polyacrylonitrile as-spun fibre through a drawing-off, wash, the compacting by drying that oils, secondary
Drawing-off, thermal finalization
In the step, by polymer spinning solution obtained above through solidifying after the spinneret spinneret with shape spinneret orifice
Bath solidification draw forming is band shape polyacrylonitrile as-spun fibre, band shape polyacrylonitrile as-spun fibre through a drawing-off, wash, oil
Band shape polyacrylonitrile fibril is made after compacting by drying, secondary drawing-off, thermal finalization.Inventors have found that by using having band shape
The spinneret of spinneret orifice carries out spinning, then obtains band shape polyacrylonitrile as-spun fibre through coagulating bath solidification draw forming, then pass through
Drawing-off washes, the compacting by drying that oils, secondary drawing-off, band shape polyacrylonitrile fibril is made after thermal finalization, that is, is keeping former
In the case where silk minor axis dimension variation less, increase precursor major axis dimension, which pre-oxidized subsequent
Cheng Zhong, due to the presence of precursor short axle, so that the contracting of oxygen diffusion path is shorter, oxygen element can be easy to be diffused into original through precursor short axle
Silk is internal, obtains the pre- oxide structure of homogeneous, high-performance carbon fibre can most be prepared after being carbonized afterwards, be expected to solve traditional PAN
Fiber cross-sectional dimension limitation problem.
Specifically, polymer spinning solution obtained above is passed sequentially through the spinneret spinneret with shape spinneret orifice, solidification
Bath solidification drawing-off drawing-off, is washed, the compacting by drying that oils, secondary drawing-off and thermal finalization, wherein refers to Fig. 2, Fig. 3, spray
There are multiple band shape spinneret orifices on filament plate 1, the longitudinal axis L of spinneret orifice is 0.40~0.45mm, and short axle W is 0.050~0.055mm,
The temperature of polymer spinning solution is 50~70 degrees Celsius, and spinneret speed is 2.25~3.75m/min, and process of setting uses three-level
Coagulating bath, three-level coagulating bath are the mixed solution of dimethyl sulfoxide and water, and the concentration of level-one coagulating bath be 72~
77wt%, preferably 74wt%, temperature be 35~55 degrees Celsius, setting time be 20~50 seconds, solidification hauling speed be 1.8~
3m/min, the concentration of second level coagulating bath are 40~50wt%, preferably 45wt%, temperature room temperature, and setting time is 20~50 seconds, three
The concentration of grade coagulating bath is 10~20wt%, and preferably 15wt%, temperature room temperature, setting time is 20~50 seconds, and second level is solidifying
Gu and three-level process of setting solidification hauling speed it is identical as level-one process of setting, due to polymer spinning solution pass through spinneret orifice
It with extrusion swelling effect, is controlled by conditions above, inhibits extrusion swelling effect to form band shape poly- third in process of setting
Alkene nitrile as-spun fibre, and since strand contains a large amount of solvents, as-spun fibre deformation ratio is maximum, and preferably control solidification draw ratio is
0.8,3~9 times of multiplying power with the drawing-off in boiling water of shape polyacrylonitrile as-spun fibre obtained through solidification, preferably 4.5~7 times
The short axle of (relative to three-level coagulating bath speed is left) control fiber is 15~22 μm, and long axis is 55~85 μm, then carries out water
It washes, water-washing process uses gradient increased temperature, is successively that 10~25 are washed in 50,60,65,70,75,80 C water baths in temperature
Second, control washing total time is 60~150 seconds, and fiber, which is oiled, after washing is dried densification, and drying temperature is 110 Celsius
Degree, time are 30~45 seconds, and fiber carries out secondary drawing-off, secondary draft ratio in overheated steam or high-temperature steam after drying
It is 2.0~4.0 times, preferably 2.2~2.8 times, the short axle of fiber is 10.6~11.4 μm after secondary drawing-off, and long axis is 30~33 μ
Then m carries out thermal finalization, obtain band shape polyacrylonitrile fibril, the fiber number with shape polyacrylonitrile fibril be 0.30~
0.36tex, is 4 times of circular cross-section polyacrylonitrile fibril fiber number, and a band shape monofilament is equivalent to 4 circular cross-section monofilament.
It should be noted that the other conditions of spinning process by those skilled in the art determine according to actual needs, herein not
It repeats again.
S3: will be with shape polyacrylonitrile fibril through pre-oxidation, low-temperature carbonization and high temperature cabonization
In the step, by band shape polyacrylonitrile fibril obtained above after pre-oxidation, low-temperature carbonization and high temperature cabonization
To banding pattern polyacrylonitrile carbon fiber.Specifically, by with shape polyacrylonitrile fibril in air atmosphere, 220~270 DEG C of pre-oxidation furnace
It carries out pre-oxidation treatment 50~100 minutes, then successively in the low-carbon furnace of 350~800 DEG C of nitrogen atmospheres, 1100~1600 DEG C
Carbonization treatment obtains band shape polyacrylonitrile carbon fiber in the high-carbon furnace of nitrogen atmosphere.The band shape polyacrylonitrile for taking this method to prepare
22.3~24.2 microns of carbon fiber long axis, short axle is 5.1~5.4 microns, and fiber number is 0.154~0.174tex, and filament stretch is strong
Degree is not less than 5.4GPa, stretch modulus 294GPa, and the band tee section carbon fiber of the application is equal length circle
Nearly 4 times of section carbon fibre, carbon fiber and composite material preparation efficiency can be greatly improved.
It should be noted that pre-oxidation and the other conditions of carbonisation are true according to actual needs by those skilled in the art
Fixed, details are not described herein again.
In the second aspect of the invention, the invention proposes a kind of band shape polyacrylonitrile carbon fibers.It is according to the present invention
Embodiment, the carbon fiber are prepared using the above method.Specifically, the band shape carbon fiber long axis 22.3~24.2 is micro-
Rice, short axle are 5.1~5.4 microns, and fiber number is 0.154~0.174t tex, and monofilament tensile strength is not less than 5.4GPa, stretching die
Amount is 294GPa, and the band tee section carbon fiber of the application is nearly 4 times of circular cross-section carbon fiber, and carbon can be greatly improved
Fiber and composite material preparation efficiency.In addition, the band tee section carbon fiber is due to large specific surface area, it can be between reinforcing fiber and matrix
Binding force, keep composite property more excellent.And it is good with wetting property of the shape carbon fiber to liquid, preparing composite material
Shi Yougeng excellent composite performance.Circular monofilaments section is small, between the fiber of the composite material of identical mass fraction fiber preparation
There are many gaps, needs to be filled by resin, reduce the binding force of fiber and matrix, and the carbon fiber with tee section can be more
Good filled composite materials.
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
Acrylonitrile, methyl acrylate, itaconic acid are mixed with solvent dimethyl sulfoxide (DMSO), initiator azo two is added
Isobutyronitrile (AIBN) carries out acrylonitrile solution combined polymerization, wherein in terms of the comonomer gross mass of investment, by acrylonitrile
97.2%, the ratio of methyl acrylate 1.6% and itaconic acid 1.2% puts into monomer and comonomer into polymeric kettle, adds
DMSO solvent, control monomers acrylonitrile account for the 22% of polymerization system gross mass, 65 DEG C at a temperature of react 24 hours, gained is poly-
Solution is closed after de- single deaeration, is stored in 60 DEG C of progress wet spinnings, polymer dope pass through metering pump, candle filter,
Spinneret with shape spinneret orifice, spinneret hole number is 22, aperture is 0.05 × 0.4mm (W × L), and spinning solution passes through spinneret
The speed of plate is 3.75m/min, and sequentially entering dimethyl sulfoxide mass concentration is respectively 74%, 45%, 15% by dimethyl
The three-level coagulating bath system of sulfoxide and water composition, level-one coagulation bath temperature are 45 DEG C, and second level and three-level coagulating bath are room temperature, are carried out
Multistage is formed at fibre, and it is 3m/min that strand, which leaves level-one, second level and three-level coagulating bath speed, and solidification drawing-off (is defined as strand
Leave coagulating bath speed and spinneret velocity ratio) it is 0.8, it obtains band shape and solidifies strand, by drawing-off of boiling water, a drawing-off
The strand that multiple is 4.5 times carries out multi-stage water wash, and washing uses gradient increased temperature, and temperature is followed successively by 50,60,65,70,75,80 DEG C,
Total time 90s is washed, then oils and carries out the drying of multiple roll hot-rolling, drying temperature is 110 DEG C, dry total time 40s；Using mistake
2.27 times of the secondary drawing-off of hot steam obtains polyacrylonitrile fibril (its Cross Section Morphology is as shown in Figure 4) through thermal finalization, precursor warp
Under air atmosphere, carried out at pre-oxidation in six pre-oxidation furnaces that temperature is respectively 220,230,240,250,260 and 270 DEG C
Reason, preoxidation time 90 minutes；In a nitrogen atmosphere, temperature is respectively 350,450 and 800 DEG C of three-temperature-zone low temperature carbonization furnace
Processing；In a nitrogen atmosphere, temperature is respectively 1100,1600 DEG C of two warm area high temperature carbonization furnaces processing, obtains carbon fiber, breaks
Face pattern is as shown in Figure 5A, and surface topography is as shown in Figure 5 C.
Embodiment 2
It is fed into polymeric kettle according to the polymerization formula of embodiment 1, polymerization reaction is carried out using same process conditions, takes off
Single, deaeration obtains spinning solution.By 1 spinneret of embodiment, solidification, a drawing-off, washes, oils, compacting by drying, compacting by drying
Fiber afterwards obtains polyacrylonitrile fibril through thermal finalization using 2.41 times of the secondary drawing-off of overheated steam.The precursor is through air
Under atmosphere, pre-oxidation treatment is carried out in six pre-oxidation furnaces that temperature is respectively 220,230,240,250,260 and 270 DEG C, in advance
Oxidization time 80 minutes；In a nitrogen atmosphere, temperature is respectively 350,450 and 800 DEG C of three-temperature-zone low temperature carbonization furnace processing；
In a nitrogen atmosphere, temperature is respectively 1100,1600 DEG C of two warm area high temperature carbonization furnaces processing, obtains carbon fiber, section shape
Looks are as shown in Figure 5 B.
Embodiment 3
It is fed into polymeric kettle according to the polymerization formula of embodiment 1, polymerization reaction is carried out using same process conditions, takes off
Single, deaeration obtains spinning solution.By 1 spinneret of embodiment, solidification, a drawing-off, washes, oils, compacting by drying, compacting by drying
Fiber afterwards obtains polyacrylonitrile fibril through thermal finalization using 2.50 times of the secondary drawing-off of overheated steam.The precursor is through air
Under atmosphere, pre-oxidation treatment is carried out in six pre-oxidation furnaces that temperature is respectively 220,230,240,250,260 and 270 DEG C, in advance
Oxidization time 70 minutes；In a nitrogen atmosphere, temperature is respectively 350,450 and 800 DEG C of three-temperature-zone low temperature carbonization furnace processing；
In a nitrogen atmosphere, temperature is respectively 1100,1600 DEG C of two warm area high temperature carbonization furnaces processing, obtains carbon fiber.
Embodiment 4
It is fed into polymeric kettle according to the polymerization formula of embodiment 1, polymerization reaction is carried out using same process conditions, takes off
Single, deaeration obtains spinning solution.By 1 spinneret of embodiment, solidification, a drawing-off, washes, oils, compacting by drying, compacting by drying
Fiber afterwards obtains polyacrylonitrile fibril through thermal finalization using 2.62 times of the secondary drawing-off of overheated steam.The precursor is through air
Under atmosphere, pre-oxidation treatment is carried out in six pre-oxidation furnaces that temperature is respectively 220,230,240,250,260 and 270 DEG C, in advance
Oxidization time 60 minutes；In a nitrogen atmosphere, temperature is respectively 350,450 and 800 DEG C of three-temperature-zone low temperature carbonization furnace processing；
In a nitrogen atmosphere, temperature is respectively 1100,1600 DEG C of two warm area high temperature carbonization furnaces processing, obtains carbon fiber.
Comparative example
It is initiator with azodiisobutyronitrile (AIBN), with dimethyl sulfoxide (DMSO) for solvent, carries out acrylonitrile solution
Combined polymerization.It is put into 97.2% acrylonitrile of mass concentration, 1.6% methyl acrylate and 1.2% itaconic acid ratio into polymeric kettle
Monomers acrylonitrile and comonomer methyl acrylate and itaconic acid, add solvent DMSO, and control monomers acrylonitrile accounts for condensate
The mass concentration of system is 22%, 65 DEG C at a temperature of react 24 hours, gained polymeric solution is put into 60 DEG C of storages through de- single deaeration
Wet spinning is carried out in material kettle.Using 0.05 aperture, the spinneret of 1000 hole counts, spinneret speed is 3.75m/min, in coagulating bath
(being made of dimethyl sulfoxide and water) dimethyl sulfoxide concentration is respectively 74% (one is solidifying), 45% (two is solidifying), 15% (three is solidifying) three
Gradient freeze forms in a coagulating tank, and leaving a solidifying coagulating bath speed is 3m/min, level-one, second level and three-level coagulation bath temperature
Respectively 45 DEG C, 25 DEG C, 25 DEG C, it is dry (dry by 4.5 times of drawing-off of boiling water, washing (60 DEG C of washing temperature), the hot-rolling that oils
110 DEG C of dry temperature), using the secondary drawing-off of overheated steam, 2.2 times of secondary drawing-off obtains polyacrylonitrile fibril through thermal finalization.
The precursor is through under air atmosphere, being respectively 220,230,240,250,260 and 270 DEG C of six pre-oxidation furnaces in temperature
Middle carry out pre-oxidation treatment, preoxidation time 60 divide, at the three-temperature-zone low temperature carbonization furnace of 350,450,800 DEG C of nitrogen atmosphere
Reason is handled in two warm area high temperature carbonization furnaces of 1100,1600 DEG C of nitrogen atmospheres, the carbon fiber surface pattern and cross-section morphology
Electromicroscopic photograph difference is as shown in Figure 6 A and 6B, and calculating carbon fiber diameter according to scale is 5.4 μm.
Embodiment 1-4 and the performance of polyacrylonitrile fibril obtained by comparative example and carbon fiber are as shown in table 1.
1 polyacrylonitrile fibril of table and carbon fiber performance
Claims (10)
1. a kind of method prepared with shape polyacrylonitrile carbon fiber, wherein include:
(1) acrylonitrile monemer and itaconic acid, methyl acrylate and solvent are subjected to combined polymerization, it is molten to obtain polymer spinning
Liquid；
(2) it is through coagulating bath solidification draw forming after the spinneret spinneret with shape spinneret orifice by the polymer spinning solution
Band shape polyacrylonitrile as-spun fibre, the band shape polyacrylonitrile as-spun fibre through a drawing-off, wash, the compacting by drying that oils,
Band shape polyacrylonitrile fibril is made after secondary drawing-off, thermal finalization；
(3) by the band shape polyacrylonitrile fibril through pre-oxidation, low-temperature carbonization and high temperature cabonization, to obtain banding pattern polyacrylonitrile
Carbon fiber.
2. according to the method described in claim 1, wherein, in step (2), there are multiple band shape spinnerets on the spinneret
Hole, the long axis of the spinneret orifice are 0.40~0.45mm, and short axle is 0.050~0.055mm.
3. according to the method described in claim 1, wherein, in step (2), the temperature of the polymer spinning solution is 50~
70 degrees Celsius, the spinneret speed is 2.25~3.75m/min,
Optional, described be set in three-level coagulating bath carries out, and it is 1.8~3m/min, level-one solidification that level-one, which solidifies draft speed,
Bath temperature is 35~55 degrees Celsius.
4. according to the method described in claim 1, wherein, in step (2), the long axis with shape polyacrylonitrile as-spun fibre
It is 390~440 microns, short axle is 49~64 microns.
5. according to the method described in claim 1, wherein, in step (2), the draft ratio of a drawing-off is 3~9
Times, preferably 4.5~7 times.
6. according to the method described in claim 5, wherein, in step (2), after a drawing-off, the long axis of fiber is
55~85 microns, short axle is 15~22 microns.
7. according to the method described in claim 1, wherein, in step (2), the draft ratio of the secondary drawing-off is 2~4
Times, preferably 2.2~2.8 times,
Optional, after the secondary drawing-off, the long axis of fiber is 30~33 microns, and short axle is 10.6~11.4 microns.
8. according to the method described in claim 1, wherein, in step (2), the fiber number with shape polyacrylonitrile fibril is
0.30~0.36tex.
9. a kind of band shape polyacrylonitrile carbon fiber, wherein the band shape polyacrylonitrile carbon fiber is using any in claim 1-8
Method described in is prepared.
10. carbon fiber according to claim 9, wherein the carbon fiber long axis is 22.3~24.2 microns, and short axle is
5.1~5.4 microns, fiber number is 0.154~0.174tex, and monofilament tensile strength is not less than 5.4GPa, stretch modulus 294GPa.
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