CN110373729A - As-spun fibre, polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre and preparation method - Google Patents

As-spun fibre, polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre and preparation method Download PDF

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Publication number
CN110373729A
CN110373729A CN201910718257.3A CN201910718257A CN110373729A CN 110373729 A CN110373729 A CN 110373729A CN 201910718257 A CN201910718257 A CN 201910718257A CN 110373729 A CN110373729 A CN 110373729A
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polyacrylonitrile
fibre
spun
spun fibre
preparation
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CN201910718257.3A
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CN110373729B (en
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刘耀东
周普查
吕春祥
安锋
于毓秀
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02Heat treatment
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/06Wet spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/12Stretch-spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/12Stretch-spinning methods
    • D01D5/14Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/40Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21Carbon 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
    • D01F9/22Carbon 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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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention relates to a kind of as-spun fibre, polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre and preparation methods.The technical solution mainly used are as follows: the as-spun fibre is the strand with fibre morphology that polyacrylonitrile dynamic analysis of spinning obtains after coagulating bath shapes;Wherein, the light transmittance of the as-spun fibre is not less than 60%.Present invention generally provides or prepare the as-spun fibre that a kind of light transmittance is greater than 60%, and the structure of the as-spun fibre under the light transmittance is uniform, so that the polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre that structure is uniform, has excellent performance can be prepared using the preparation method of the as-spun fibre or the as-spun fibre.

Description

As-spun fibre, polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre and preparation method
Technical field
The present invention relates to a kind of fibre technology fields, more particularly to a kind of as-spun fibre, polyacrylonitrile fibre, polypropylene Itrile group carbon fiber and preparation method.
Background technique
Polyacrylonitrile-based carbon fibre has the excellent performances such as high specific strength, high ratio modulus, using it as reinforcing fiber Composite material is used widely in aerospace, new energy etc..With the extension of carbon fiber application field, to polypropylene The performance requirement of itrile group carbon fiber further increases.
The structure feature of polyacrylonitrile fibre (that is, carbon fiber precursor fiber) determines the base of polyacrylonitrile-based carbon fibre This structure.Larger impact of the polyacrylonitrile-based carbon fibre performance by polyacrylonitrile fibre performance.Particularly, when polyacrylonitrile fibre For the structure of dimension there are when skin-core structure or uneven structure, the performance of polyacrylonitrile-based carbon fibre can considerable decrease.
And as-spun fibre is the basis of polyacrylonitrile fibre structure.Polyacrylonitrile fibre is dynamic analysis of spinning by being frozen into Shape obtains as-spun fibre, as-spun fibre is prepared using processes such as aftertreatment technologies.Wherein, as-spun fibre is thin by spinning Stream slowly forms fibre morphology acquisition in coagulating bath.Fiber forming process of the dynamic analysis of spinning in coagulating bath directly determines The structure of as-spun fibre.
It in the prior art, is that as-spun fibre form is formed by phase separation after dynamic analysis of spinning enters coagulating bath; Since phase separation is at first since the surface layer of fiber, this has differences the surface structure of fiber and core structure, And then cause so-called " skin-core structure " to exist, the structure of as-spun fibre it is uneven, make polyacrylonitrile fibre, pan based fibers Structure it is uneven, while also reducing the performance of polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre.
Summary of the invention
In view of this, the present invention provides a kind of as-spun fibre, polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre and preparation side Method, main purpose are to improve the structural homogeneity of as-spun fibre, to obtain the preferable polyacrylonitrile fibre of structural homogeneity energy And polyacrylonitrile-based carbon fibre.
In order to achieve the above objectives, present invention generally provides following technical solutions:
On the one hand, the embodiment of the present invention provides a kind of as-spun fibre, wherein the as-spun fibre is polyacrylonitrile spinning The strand with fibre morphology that thread obtains after coagulating bath shapes;Wherein, the light transmittance of the as-spun fibre is not less than 60%.
Preferably, the average pore size at the surface structure of the as-spun fibre is the first average pore size;The as-spun fibre Core structure at average pore size be the second average pore size;Wherein, first average pore size and the second average pore size is inclined Difference is within 10%.It preferably, is the most short distance between fiber outer profile on fiber radial section at the surface structure At the position no more than 1 micron;At the core structure on fiber radial section between radial section center of gravity most At position of the short distance no more than 1 micron.
On the other hand, the preparation method of above-mentioned as-spun fibre, includes the following steps:
Spinneret: polyacrylonitrile spinning solution is squeezed out by spinneret orifice, forms polyacrylonitrile dynamic analysis of spinning;
Forming: forming processing of the polyacrylonitrile dynamic analysis of spinning Jing Guo coagulating bath obtains as-spun fibre;Wherein, described The temperature of coagulating bath is -50~10 DEG C.
Preferably, residence time of the polyacrylonitrile dynamic analysis of spinning in the coagulating bath is 2-60 seconds.
Preferably, the polymer in the polyacrylonitrile spinning solution is polyacrylonitrile homopolymer, polyacrylonitrile copolymer One or both of mixture.Preferably, the solvent in the polyacrylonitrile spinning solution is dimethyl sulfoxide, dimethyl One or more of formamide, dimethyl acetamide, lithium chloride solution, ionic liquid, sodium thiocyanate solution, liquor zinci chloridi Mixture.
Preferably, the coagulating bath includes the non-solvent and solvent that mass ratio is 1:0~2:8, and the non-solvent is opposite Polymer in the polyacrylonitrile spinning solution has the set value of 2-150.The mass ratio of the non-solvent and solvent is excellent It is selected as 1:0~3:7, further preferably 9:1~4:6, is still more preferably 8:2~4:6;Preferably, the non-solvent is Formic acid, glycerol, ethylene glycol, acetic acid, ethyl alcohol, methanol, chloroform, isobutanol, isoamyl alcohol, butanediol, benzyl alcohol, carbon tetrachloride, first The mixture of one or more of benzene, acetone, water, dioxane.
Preferably, polyacrylonitrile spinning solution is made by the as-spun fibre using wet spinning process;Wherein, spinning head is led Stretching multiple is 0.7~1.5 times, preferably 0.75~1.2 times, further preferably 0.8~1.1 times;Or using dry spray Wet-spinning The as-spun fibre is made in polyacrylonitrile spinning solution by silk method;Wherein, spinneret draft multiple be 2~12 times, preferably 3~ 8 times, further preferably 4~6 times.
On the other hand, the embodiment of the present invention also provides a kind of polyacrylonitrile fibre, and the polyacrylonitrile fibre is by above-mentioned As-spun fibre be prepared.Preferably, at the average pore size at the surface structure of the polyacrylonitrile fibre and core structure Average pore size between deviation within 10%;Preferably, the tensile strength of the polyacrylonitrile fibre is 900MPa- 1.4GPa, preferably 950-1.5GPa.
Here, the polyacrylonitrile fibre is applied not only to prepare carbon fiber, the reinforcement material of composite material can also be used as Material or industrial yarn.It specifically,, can be with other than preparing carbon fiber since the polyacrylonitrile fibre mechanical property is preferable It is used separately as reinforcement fiber, such as building enhancing, enhancing concrete, being woven to polyacrylonitrile band is that hawser etc. uses.
On the other hand, the preparation method of above-mentioned polyacrylonitrile fibre, includes the following steps:
It prepares as-spun fibre: the as-spun fibre is prepared using the preparation method of above-mentioned as-spun fibre;
Drawing-off processing: in gas medium, drawing-off processing is carried out to the as-spun fibre;Wherein, on the as-spun fibre The as-spun fibre stated;
Post-processing: treated that as-spun fibre is post-processed for counter extensioin, obtains polyacrylonitrile fibre.
Preferably, the step of post-processing, comprising: counter extensioin treated as-spun fibre carries out washing process, stretches Processing, oiling treatment, drying process, obtain polyacrylonitrile fibre.
Preferably, in the step of drawing-off is handled:
The drawing-off handles the drawing-off processing that is positive;Preferably, to the as-spun fibre apply drafting multiple be 1.05~ 3.5 times, preferably 1.2~3 times, further preferably 1.5~2 times;And/or
The temperature of the gas medium is not higher than 25 DEG C;The temperature of the gas medium is not less than the glass of the as-spun fibre The solvent-laden cryogenic temperature of institute in glass temperature, as-spun fibre;And/or
The gas medium is any one of air, nitrogen, vapor, inert gas, carbon dioxide.
In another aspect, also a kind of polyacrylonitrile-based carbon fibre of the embodiment of the present invention, the polyacrylonitrile-based carbon fibre is by upper The polyacrylonitrile fibre stated is prepared.Preferably, the average pore size at the surface structure of the polyacrylonitrile-based carbon fibre with The deviation between average pore size at core structure is within 10%;It is further preferred that the polyacrylonitrile-based carbon fibre The deviation between the average pore size at average pore size and core structure at surface structure is within 5%;Preferably, described poly- third The tensile strength of alkene itrile group carbon fiber is 7.4-9GPa.
In another aspect, the preparation method of above-mentioned polyacrylonitrile-based carbon fibre, includes the following steps: to above-mentioned polypropylene Nitrile fiber is heat-treated, and polyacrylonitrile-based carbon fibre is obtained;
Preferably, it is described heat treatment include: the polyacrylonitrile fibre is pre-oxidized, low-temperature carbonization, high temperature cabonization Processing;It is further preferred that the temperature of the pre-oxidation is 185~350 DEG C;Preferably, the temperature of the low-temperature carbonization processing It is 400~850 DEG C;Preferably, the temperature of the high temperature cabonization is 1200~3000 DEG C.
Compared with prior art, as-spun fibre of the invention, polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre and preparation side Method at least have it is following the utility model has the advantages that
1. the embodiment of the present invention provides a kind of as-spun fibre, the light transmittance of the as-spun fibre is not less than 60%;The present invention is real As-spun fibre of this light transmittance more than or equal to 60% for applying example means that its structural homogeneity is good.
Further, the average pore size at the surface structure of as-spun fibre provided in an embodiment of the present invention is the first average hole Diameter;Average pore size at the core structure of as-spun fibre is the second average pore size;Wherein, first average pore size and second flat The deviation in equal aperture is within 10%.It can be seen that the structural homogeneity of as-spun fibre provided in an embodiment of the present invention is preferable.
2. the embodiment of the present invention provides a kind of preparation method of as-spun fibre, pass through the ingredient of control coagulating bath, solidification The temperature and fiber of bath control the light transmittance of formed as-spun fibre, make it not less than 60% in the residence time of coagulating bath, Improve the uniformity of as-spun fibre.
3. the embodiment of the present invention also provides the preparation method of a kind of polyacrylonitrile fibre and polyacrylonitrile fibre, wherein should Polyacrylonitrile fibre is prepared by above-mentioned as-spun fibre, and since the structure of as-spun fibre used is uniform, then the present invention is implemented The structure of the polyacrylonitrile fibre of example preparation is uniform, and has excellent performance.
Further, in the preparation method of polyacrylonitrile fibre provided in an embodiment of the present invention, by forming nascent fibre After the step of dimension, before being post-processed to as-spun fibre and (including the steps that washing, stretch, oil, drying process): increasing If the step of carrying out positive drawing-off processing in gas medium to as-spun fibre, in this way, tension can be applied to as-spun fibre, first While life fibre morphology strand is elongated, extrusion effect is formed to the solvent contained by strand inside, forces solvent contained by strand It is exuded to strand surface, the solvent of exudation forms drop and leaves strand, to reach the technology effect of partial solvent in removal strand Fruit, to reduce the wastewater flow rate of subsequent washing process.
4. the embodiment of the present invention also provides the preparation method of a kind of polyacrylonitrile-based carbon fibre and polyacrylonitrile-based carbon fibre, Wherein, which is prepared by above-mentioned polyacrylonitrile fibre, since the structure of polyacrylonitrile used is equal Even, then the structure of the polyacrylonitrile-based carbon fibre of preparation of the embodiment of the present invention is uniform, and has excellent performance.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention, And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is the image of the as-spun fibre tow in the embodiment of the present invention 1 when preparing as-spun fibre, in coagulating basin.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with Specific embodiment, structure, feature and its effect applied according to the present invention is described in detail such as in attached drawing and preferred embodiment Afterwards.In the following description, what different " embodiment " or " embodiment " referred to is not necessarily the same embodiment.In addition, one or more Special characteristic, structure or feature in a embodiment can be combined by any suitable form.
On the one hand, the embodiment of the present invention provides a kind of as-spun fibre;Wherein, as-spun fibre is polyacrylonitrile dynamic analysis of spinning warp The strand with fibre morphology obtained after supersolidification bath;Wherein, the light transmittance of the as-spun fibre provided in the present embodiment is not low In 60%.
Here, as-spun fibre (that is, coagulated yarn) is formed after referring to the forming of polyacrylonitrile polymer thread with fibre morphology Strand;Polymer in the strand can be in curdled appearance, can be gel state, can also be and is partially in solidification shape State or gel state.
The inventors found that: after polyacrylonitrile polymer solution enters coagulating bath, since mass transfer and/or heat transfer are made With so that polyacrylonitrile polymer solution becomes non-solution state from solution state, the light transmittance of polymer solution can drop at this time It is low.When polyacrylonitrile polymer thread forms coagulated yarn (that is, as-spun fibre) of fibre morphology, if the light transmittance of coagulated yarn Greatly, then the structure in coagulated yarn is uniform.Also, when as-spun fibre of the invention leaves coagulating bath light transmittance be more than or equal to 60%.Transmitance is lower than 60% when if as-spun fibre leaves coagulating bath, the structural homogeneity of as-spun fibre is poor at this time.
It should be noted that: the uniform as-spun fibre of structure (that is, coagulated yarn) refers to the surface structure of as-spun fibre In the reasonable scope with the difference of core structure, specifically, average hole at average pore size and core structure at surface structure Deviation between diameter is within 10%.
Preferably, do not surpass at the surface structure for the shortest distance between fiber outer profile on fiber radial section It crosses at 1 micron of position;It is the shortest distance between radial section center of gravity on fiber radial section at the core structure At position no more than 1 micron.Specifically, at surface structure is defined as: refer in the section of fiber radial direction, from outer profile to Range within 1 micron of inside.Definition at core structure is to refer in fiber radial section, using the center of gravity of radial section as The range of circle within medium-sized 1 micron of diameter.
Definition at above-mentioned surface structure, at core structure is applicable not only to as-spun fibre, applies also for polyacrylonitrile fibre Dimension, polyacrylonitrile-based carbon fibre.
Here, the test method of the average pore size of the surface structure and core structure of as-spun fibre is:
1, first with the dry as-spun fibre of freeze-drying, dry as-spun fibre sample is obtained;
2, the cross-sectional image that as-spun fibre is obtained using transmission electron microscope or scanning electron microscope etc., can before test To carry out metal spraying processing to as-spun fibre sample, or other are carried out to as-spun fibre it can increase observing effect but do not change solidifying Gu the pre-treatment of the original pattern of silk;
3, coagulated yarn micro image is handled using image processing software, obtains the pore-size distribution of different zones.Choosing It selects at the 1000nm inwards of as-spun fibre surface, diameter is representative region of the border circular areas of 200nm as surface structure area, The hole of the first two major diameter is removed when calculating the average pore size at surface structure, and calculating, to reduce error.Select as-spun fibre Radial section center of gravity diameter is representative region of the border circular areas of 200nm as core structure, is calculated flat at core structure Equal aperture, when calculating, removes the hole of the first two major diameter, to reduce error.
In addition, the application tests the light transmission of (can also be with on-line testing) as-spun fibre when as-spun fibre leaves coagulating bath Rate, using light transmittance tester on-line testing as-spun fibre light transmittance obtained, optical source wavelength is 500 ± 10nm when test, Gained light transmittance be fiber sample ulking thickness be 1 ± 0.1mm when light transmittance.
On the other hand, the embodiment of the invention also provides the preparation methods of above-mentioned as-spun fibre comprising following steps:
1) spinneret: polyacrylonitrile spinning solution is squeezed out by spinneret orifice, forms polyacrylonitrile dynamic analysis of spinning.
In this step, the polymer in polyacrylonitrile spinning solution can be acrylonitrile homopolymer or be with propylene Nitrile copolymer as main component and polymer is obtained with acrylonitrile homopolymer or with acrylonitrile copolymer as main component Blend as main component.
In this step, the solvent in polyacrylonitrile spinning solution (referred to as polyacrylonitrile solvent);Selection dimethyl sulfoxide, Dimethylformamide, dimethyl acetamide, lithium chloride/ionic liquid, sodium thiocyanate solution, it is any in liquor zinci chloridi or on State several mixtures.
In this step, the molecular chain conformation of the polymer in polyacrylonitrile spinning solution is not particularly limited, molecule Measure smaller carbon fiber precursor fiber obtained and carbon fiber mechanical property be poorer, thus polymer molecular weight preferably 100,000 with On.The more big carbon fiber precursor fiber obtained of molecular weight and carbon fiber mechanical property are better, but the polymer of macromolecule Dissolubility in a solvent is poor, therefore the upper limit of polymer molecular weight is not particularly limited, as long as polymer can be dissolved in In solvent, usual polymer is below 1,500,000.
2) shape: forming processing of the polyacrylonitrile dynamic analysis of spinning Jing Guo coagulating bath obtains as-spun fibre;.
In this step, coagulation bath temperature is -50~10 DEG C.Under this condition, polymer solution solidifies in coagulating bath Speed is slower, inside and outside as-spun fibre uniform, light transmittance is high easy to form.
In this step, the bath foam of the coagulating bath include mass ratio be 1:0~2:8 non-solvent (polyacrylonitrile is non-molten Agent: the solvent of polyacrylonitrile cannot be dissolved) and solvent (solvent of polyacrylonitrile polyacrylonitrile solvent: can be dissolved), and it is described Non-solvent has the set value of 2-150 relative to the polymer in the polyacrylonitrile spinning solution.The non-solvent and solvent Mass ratio be preferably 1:0~3:7, further preferably 9:1~4:6 is still more preferably 8:2~4:6;Preferably, institute Stating non-solvent is formic acid, glycerol, ethylene glycol, acetic acid, ethyl alcohol, methanol, chloroform, isobutanol, isoamyl alcohol, butanediol, benzyl alcohol, four The mixture of any one or more of chlorination carbon, toluene, acetone, water, dioxane;Preferably, molten in the coagulating bath Agent is polyacrylonitrile solvent, selects dimethyl sulfoxide, dimethylformamide, dimethyl acetamide, lithium chloride/ionic liquid, sulphur Any or above-mentioned several mixture in cyanic acid sodium solution, liquor zinci chloridi.
Here, removing solvent and non-solvent in component in coagulating bath, effect of the invention can not also be damaged comprising other Other components, be exactly in addition to the solvent and non-solvent listed in coagulating bath, there may also be other components.
Here, controlling the light transmittance of formed as-spun fibre by the ingredient of control coagulating bath, the temperature of coagulating bath, making It is not less than 60%, improves the uniformity of as-spun fibre.
Under the above conditions, polyacrylonitrile dynamic analysis of spinning occurs that gel state can be preferentially formed before mutually separating in coagulating bath, Or mutually separation and gelation process carry out simultaneously, so that the as-spun fibre external and internal compositions formed are essentially identical, to obtain nothing Skin-core structure, the as-spun fibre to homogenize are (here, the gelation process refers to that polymer solution is changed into from solution state The process of gel state;The loss modulus of polymer solution is greater than storage modulus, and the gel state refers to polymer solution at certain State when its loss modulus is equal to or less than storage modulus in one transition process, but polymer solution still has part not send out It is raw mutually to separate.).
It should be noted that: above-mentioned " set value " refers to solution required for dilute polymer turbidimetric titration Volume.Specific method is: 1, dissolving polymer first with solvent, obtain the homogeneous solution that concentration is 1wt%;2, it is stirring Mix, temperature by under the conditions of 20 DEG C to the step 1 of certain volume amount obtain polymer solution in other solution are added dropwise, record and work as The volume for the solution being added dropwise when first appearing cloud point in system;3, by calculating, acquisition makes in 100ml polymer solution for the first time There is the bulking value for the solution being added dropwise when cloud point, which is defined as solidification of the solution to this polymer Value.Where it determines that solvent used in set value is dimethylformamide.
Preferably, polyacrylonitrile dynamic analysis of spinning in the residence time in coagulating bath between 2-60 seconds, polyacrylonitrile spinning Thread residence time in coagulating bath is greater than 60 seconds, and polymer solution residence time in coagulating bath is too long, reduces production efficiency. Polyacrylonitrile dynamic analysis of spinning is when the residence time was less than 2 seconds in coagulating bath, and coagulated yarn goes out after coagulating basin to be easy to be adhered between fiber.
In addition, the preparation process of above-mentioned as-spun fibre can be any one in wet spinning or dry-jet wet spinning. When wherein, using wet spinning, spinneret draft multiple can be 0.7~1.5 times, preferably 0.75~1.2, further preferably 0.8~1.1;When using dry-jet wet spinning, spinneret draft multiple can be 2~12 times, preferably 3~8, further preferably 4~6.
Here, in this application, term " spinneret draft multiple " to those skilled in the art, refers to: spray After silk, the velocity ratio of first speed for being actively driven rod and spinning solution thread outflow spinneret orifice.
In another aspect, the embodiment of the present invention also provides a kind of polyacrylonitrile fibre, the polyacrylonitrile fibre is at the beginning of above-mentioned Raw fiber is prepared.Preferably, the preparation method of the polyacrylonitrile fibre includes the following steps:
1) it prepares as-spun fibre: adopting and prepare the as-spun fibre with the aforedescribed process;
2) drawing-off is handled: in gas medium, carrying out drawing-off processing to the as-spun fibre;
3) post-process: treated that as-spun fibre is post-processed for counter extensioin, obtains polyacrylonitrile fibre.
Here, in the step of drawing-off is handled: the drawing-off handles the drawing-off processing that is positive;Preferably, to described first The drafting multiple that raw fiber applies is 1.05~3.5 times, preferably 1.2~3 times, further preferably 1.5~2 times;And/or institute The temperature of gas medium is stated not higher than 25 DEG C;The temperature of the gas medium not less than the as-spun fibre glass transition temperature, The solvent-laden cryogenic temperature of institute in as-spun fibre;And/or the gas medium is air, nitrogen, vapor, inert gas, two Any one of carbonoxide.
Here, by before being post-processed (including washing, stretch, oil, drying process) to as-spun fibre, it is first right As-spun fibre carries out positive drawing-off processing in gas medium, i.e., applies tension to as-spun fibre, becomes in as-spun fibre form strand While long, extrusion effect is formed to the solvent contained by strand inside, solvent contained by strand is forced to be exuded to strand surface, is seeped Solvent out forms drop and leaves strand, reaches the technical effect of partial solvent in removal strand;And then reduce subsequent washing work The wastewater flow rate of skill.
Preferably, the step of post-processing, comprising: counter extensioin treated as-spun fibre carries out washing process, stretches Processing, oiling treatment, drying process, obtain polyacrylonitrile fibre.Further preferably in the drying process process of post-processing On the basis of increase compacting by drying technique, vapor draft process, dry heat drafting technique.Here, after heretofore described The technique of processing is (drawing-off in washing, bath, oiling process, drying process, compacting by drying technique, vapor draft process, xeothermic Draft process etc.) it can be according to process optimization adjusting process sequence.Preferably, connection is glued between fiber in order to prevent in bath after drawing-off, Electrostatic is reduced, increases the convergence and fiber separation of fibre bundle, preferably carries out oiling treatment after the fiber strand silk of counter extensioin.Increase When drafting multiple, molecule is easy along fiber axial direction orientations, and fibre property increases.Therefore, in the system of pan based fibers During standby, total draft multiple is preferably 10 times more than and less than 350 times, and further preferred 25 times more than and less than 150 times.
In another aspect, the embodiment of the present invention also provides a kind of polyacrylonitrile-based carbon fibre;Wherein, polyacrylonitrile-based carbon fibre It is prepared by above-mentioned polyacrylonitrile fibre.
Preferably, the manufacturing method of polyacrylonitrile-based carbon fibre preferably includes following process: to above-mentioned polyacrylonitrile-radical Fiber is heat-treated.Heat treatment process described herein, as long as carbon fiber precursor fiber can be made to become carbon by heating Fiber is not particularly limited, such as can be pre-oxidation process, low-temperature carbonization technique, high temperature cabonization technique.
Preferably, polyacrylonitrile fibre successively obtains polyacrylonitrile-based carbon fibre by following technique: pre-oxidation process, By the pan based fibers of above-mentioned acquisition 185~350 DEG C at a temperature of oxidizing atmosphere in pre-oxidize;Low-temperature carbonization Fiber obtained in pre-oxidation process is carried out low-temperature carbonization in inert atmosphere at a temperature of 400~850 DEG C by technique;Pyrocarbon The fiber obtained in low-temperature carbonization technique is carbonized in inert atmosphere by chemical industry skill at a temperature of 1200~3000 DEG C.
It, can be by being electrolysed to carbon fiber in order to increase the bond strength of matrix in polyacrylonitrile-based carbon fibre and composite material Dimension table face is handled.After electrolysis processing, in order to increase carbon fiber convergence and subsequent service performance, carbon fiber can be carried out Slurry processing.Sizing agent used in starching processing is selected according to the type of matrix in composite material.
Average pore size at the surface structure of the polyacrylonitrile fibre of above method preparation and the average hole at core structure Deviation between diameter is within 10%, it can be seen that, the structure of the polyacrylonitrile fibre is uniform.And the polyacrylonitrile fibre Tensile strength is greater than 800MPa;Preferably greater than 1GPa, preferably 950 MPa-1.5GPa.Herein, it should be noted that due to The polyacrylonitrile fibre mechanical property is preferable, other than preparing carbon fiber, can use separately as reinforcement fiber, such as build Enhancing is built, enhancing concrete is woven to polyacrylonitrile band as the use such as hawser.
It is flat at average pore size and core structure at the surface structure of the polyacrylonitrile-based carbon fibre of above method preparation Deviation between equal aperture is within 10%, it can be seen that, the structure of the polyacrylonitrile-based carbon fibre is uniform.Preferably, described The tensile strength of polyacrylonitrile-based carbon fibre is 7.4-9GPa.
It is further described below below by specific experiment embodiment:
Embodiment 1
The present embodiment is specific to prepare mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre Steps are as follows:
1) prepared by spinning solution: using dimethyl sulfoxide as solvent, passing through solution using acrylonitrile and itaconic acid as comonomer Polymerizeing the polymer solution obtained is polyacrylonitrile spinning solution, and weight average molecular weight is 130,000, and viscosity is 90Pa.s (here, originally Embodiment and following embodiments are mainly for the polyacryl-nitrile spinning fluid of 90Pa.s for 140,000, viscosity with the viscosity average molecular weigh used Example explanation, but not limited to this, any one polyacryl-nitrile spinning fluid is suitable for the present invention).
2) prepared by as-spun fibre: using dry-jet wet spinning method, (wherein, spinneret draft multiple is that 3.5) preparation is nascent Fiber;In this step.The temperature control of coagulating bath is -15 DEG C, and the bath foam of coagulating bath includes dimethyl sulfoxide and methanol (quality Percentage is 2:8), during preparing as-spun fibre, polyacrylonitrile-radical dynamic analysis of spinning residence time in coagulating bath is 60 Second.
The light transmittance that light transmittance tester on-line testing as-spun fibre is utilized to the as-spun fibre for leaving coagulating bath, when test Optical source wavelength be 500 ± 10nm, gained light transmittance be fiber sample ulking thickness be 1 ± 0.1mm when light transmittance.
3) drawing-off is handled: carrying out drawing-off processing to as-spun fibre in air, drafting multiple is 1.2 times.
4) it post-processing step: washed with the fiber after water-bath counter extensioin, drawing-off, for water-bath fiber carry out the place that oils Then reason is dried densification using dryer roll and carries out drawing-off in high-temperature vapor;Thus make polyacrylonitrile fine It is 30 times to the total draft multiple that fiber applies in the preparation process of dimension, obtains the polyacrylonitrile that filament denier is 0.94dtex Base fiber.
5) heat treatment step: the temperature gradient for being 185~350 DEG C in temperature range by obtained polyacrylonitrile fibre It is pre-oxidized in air, obtains pre-oxidized fibers.The nitrogen gas for being 400~850 DEG C in temperature by obtained pre-oxidized fibers Low-temperature carbonization is carried out in atmosphere, obtains low-temperature carbonization fiber.The nitrogen atmosphere for being 1500 DEG C in maximum temperature by low-temperature carbonization fiber Middle carry out high temperature cabonization, and electrolysis processing is carried out as electrolyte using ammonium bisulfate solution, and washed, dried, then Starching processing is carried out, polyacrylonitrile-based carbon fibre is obtained.
Embodiment 2
The present embodiment is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, implement Example 2 the difference from embodiment 1 is that:
As-spun fibre preparation: spinneret draft multiple is 2 times;The temperature of coagulating bath is 2 DEG C;The group of coagulating bath becomes quality Than the second alcohol and water for 1:9;Residence time of the polyacrylonitrile dynamic analysis of spinning in coagulating bath is 2 seconds;
Drawing-off processing: drafting multiple is 1.5 times.
The step of other steps are with embodiment 1 is completely the same.
Embodiment 3
The present embodiment is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, implement Example 3 the difference from embodiment 1 is that:
As-spun fibre preparation: spinneret draft multiple is 3 times;The temperature of coagulating bath is -50 DEG C;The group of coagulating bath becomes second Alcohol;Residence time of the polyacrylonitrile dynamic analysis of spinning in coagulating bath is 5 seconds;
Drawing-off processing: drafting multiple is 1.4 times.
The step of other steps are with embodiment 1 is completely the same.
Embodiment 4
The present embodiment is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, implement Example 4 the difference from embodiment 1 is that:
As-spun fibre preparation: spinneret draft multiple is 8 times;The temperature of coagulating bath is 0 DEG C;The group of coagulating bath becomes first Alcohol;Residence time of the polyacrylonitrile dynamic analysis of spinning in coagulating bath is 10 seconds;
Drawing-off processing: drafting multiple is 1.6 times.
The step of other steps are with embodiment 1 is completely the same.
Embodiment 5
The present embodiment is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, implement Example 5 the difference from embodiment 1 is that:
As-spun fibre preparation: spinneret draft multiple is 4 times;The temperature of coagulating bath is -12 DEG C;The group of coagulating bath becomes matter Amount is than the formic acid and ethylene glycol for 1:9;Residence time of the polyacrylonitrile dynamic analysis of spinning in coagulating bath is 30 seconds;
Drawing-off processing: drafting multiple is 2 times.
The step of other steps are with embodiment 1 is completely the same.
Embodiment 6
The present embodiment is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, implement Example 6 the difference from embodiment 1 is that:
As-spun fibre preparation: spinneret draft multiple is 6 times;The temperature of coagulating bath is -18 DEG C;The group of coagulating bath becomes matter Amount is than the isobutanol and dimethylformamide for 6:4;Residence time of the polyacrylonitrile dynamic analysis of spinning in coagulating bath is 20 seconds;
Drawing-off processing: drafting multiple is 1.1 times.
The step of other steps are with embodiment 1 is completely the same.
Embodiment 7
The present embodiment is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, implement Example 7 the difference from embodiment 1 is that:
As-spun fibre preparation: using wet spinning process, and spinneret draft multiple is 0.7 times;The temperature of coagulating bath is 5 ℃;The group of coagulating bath becomes the isoamyl alcohol and water that mass ratio is 8:2;Residence time of the polyacrylonitrile dynamic analysis of spinning in coagulating bath It is 35 seconds;
Drawing-off processing: drafting multiple is 1.1 times.
The step of other steps are with embodiment 1 is completely the same.
Embodiment 8
The present embodiment is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, implement Example 8 the difference from embodiment 1 is that:
As-spun fibre preparation: using wet spinning process, and spinneret draft multiple is 0.75 times;Coagulation bath temperature is -25 ℃;The group of coagulating bath becomes the dimethyl sulfoxide and ethyl alcohol that mass ratio is 3:7;Polyacrylonitrile dynamic analysis of spinning stops in coagulating bath Staying the time is 25 seconds;
Drawing-off processing: drafting multiple is 1.3 times.
Other steps and embodiment 1 are completely the same.
Embodiment 9
The present embodiment is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, implement Example 9 the difference from embodiment 1 is that:
As-spun fibre preparation: using wet spinning process, and spinneret draft multiple is 0.8 times;The temperature of coagulating bath is 10 ℃;The group of coagulating bath becomes the dimethyl sulfoxide that mass ratio is 6:3:1: ethyl alcohol: water;Polyacrylonitrile dynamic analysis of spinning is in coagulating bath Residence time be 60 seconds;
Drawing-off processing: drafting multiple is 1.4 times.
Other steps and embodiment 1 are completely the same.
Embodiment 10
The present embodiment is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, implement Example 10 the difference from embodiment 1 is that:
As-spun fibre preparation: using wet spinning process, and spinneret draft multiple is 1.1 times;Coagulation bath temperature is -10 ℃;The group of coagulating bath becomes the butanediol and dimethyl acetamide that mass ratio is 3:7;Polyacrylonitrile dynamic analysis of spinning is in coagulating bath Residence time be 20 seconds;
Drawing-off processing: drafting multiple is 1.4 times.
Other steps and embodiment 1 are completely the same.
Embodiment 11
The present embodiment is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, implement Example 11 the difference from embodiment 1 is that:
As-spun fibre preparation: using wet spinning process, and spinneret draft multiple is 1.2 times;Coagulation bath temperature is -5 DEG C; The group of coagulating bath becomes propyl alcohol;Residence time of the polyacrylonitrile dynamic analysis of spinning in coagulating bath is 25 seconds;
Drawing-off processing: drafting multiple is 1.3 times.
Other steps and embodiment 1 are completely the same.
Embodiment 12
The present embodiment is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, implement Example 12 the difference from embodiment 1 is that:
As-spun fibre preparation: using wet spinning process, and spinneret draft multiple is 1.5 times;The temperature of coagulating bath is -20 ℃;The group of coagulating bath becomes ethylene glycol;Residence time of the polyacrylonitrile dynamic analysis of spinning in coagulating bath is 10 seconds;
Drawing-off processing: drafting multiple is 1.1 times.
Other steps and embodiment 1 are completely the same.
Embodiment 13
The present embodiment is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, implement Example 13 the difference from embodiment 1 is that:
As-spun fibre preparation: spinneret draft multiple is 12 times;The temperature of coagulating bath is -10 DEG C;The group of coagulating bath becomes Butanediol;Residence time of the polyacrylonitrile dynamic analysis of spinning in coagulating bath is 6 seconds;
Drawing-off processing: drafting multiple is 1.5 times.
Other steps and embodiment 1 are completely the same.
Comparative example 1
Comparative example 1 is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, compare Example 1 the difference from embodiment 1 is that: the temperature of coagulating bath is 15 DEG C, other operations similarly to Example 1.
Comparative example 2
Comparative example 2 is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, compare Example 2 the difference from example 2 is that: residence time of the polyacrylonitrile dynamic analysis of spinning in coagulating bath is 65 seconds, other and implementation Example 2 similarly operates.
Comparative example 3
Comparative example 3 is mainly for the preparation of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre;Wherein, compare Example 3 and the difference of embodiment 7 are: spinneret draft multiple is 0.55 times, other operations similarly to Example 7.
Fig. 1 is embodiment 1 when preparing as-spun fibre, the image of the as-spun fibre tow in coagulating basin.Have in coagulating basin Temperature control pipeline 3, coagulating bath 1, temperature measuring equipment 4 (thermocouple) and as-spun fibre 2.As can be seen from Figure 1: as-spun fibre 2 (referring to At position between dotted line) translucency it is especially good;It since its translucency is fine, is integrally transparent, in the comparison of coagulating bath 1 Under, it is not easy to it sees.
As-spun fibre, polyacrylonitrile fibre, the polyacrylonitrile-based carbon fibre of the preparation of embodiment 1-13 and comparative example 1-3 Structural behaviour parameter it is as shown in table 1.
Table 1 is the structural behaviour parameter of the fiber of the technological parameter and preparation of embodiment 1-13 and comparative example 1-3
As can be seen from Table 1: the light transmittance of the as-spun fibre of preparation of the embodiment of the present invention is higher, the polypropylene being made from it Nitrile fiber, the structure of polyacrylonitrile-based carbon fibre are uniform, performance is good.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, according to According to technical spirit any simple modification, equivalent change and modification to the above embodiments of the invention, this hair is still fallen within In the range of bright technical solution.

Claims (10)

1. a kind of as-spun fibre, which is characterized in that the as-spun fibre is polyacrylonitrile dynamic analysis of spinning after coagulating bath shapes The obtained strand with fibre morphology;Wherein,
The light transmittance of the as-spun fibre is not less than 60%.
2. as-spun fibre according to claim 1, which is characterized in that the average hole at the surface structure of the as-spun fibre Diameter is the first average pore size;Average pore size at the core structure of the as-spun fibre is the second average pore size;Wherein,
Deviation between first average pore size and the second average pore size is within 10%;
Preferably, it is no more than 1 at the surface structure for the shortest distance between fiber outer profile on fiber radial section At the position of micron;
It is no more than 1 micron at the core structure for the shortest distance between radial section center of gravity on fiber radial section At position.
3. the preparation method of as-spun fibre of any of claims 1 or 2, which comprises the steps of:
Spinneret: polyacrylonitrile spinning solution is squeezed out by spinneret orifice, forms polyacrylonitrile dynamic analysis of spinning;
Forming: forming processing of the polyacrylonitrile dynamic analysis of spinning Jing Guo coagulating bath obtains as-spun fibre;
Wherein, the temperature of the coagulating bath is -50~10 DEG C;
Wherein, the coagulating bath includes the non-solvent and solvent that mass ratio is 1:0~2:8;Preferably, the non-solvent relative to Polymer in the polyacrylonitrile spinning solution has the set value of 2-150;
Preferably, residence time of the polyacrylonitrile dynamic analysis of spinning in the coagulating bath is 2-60 seconds;
Preferably, the polymer in the polyacrylonitrile spinning solution is polyacrylonitrile homopolymer, in polyacrylonitrile copolymer One or two kinds of mixtures.
4. the preparation method of as-spun fibre according to claim 3, which is characterized in that
The mass ratio of the non-solvent and solvent is 1:0~3:7, preferably 9:1~4:6, further preferably 8:2~4:6; And/or
The non-solvent is formic acid, glycerol, ethylene glycol, acetic acid, ethyl alcohol, methanol, chloroform, isobutanol, isoamyl alcohol, butanediol, benzene The mixture of one or more of methanol, carbon tetrachloride, toluene, acetone, water, dioxane;And/or
Solvent in the coagulating bath is the solvent that can dissolve polyacrylonitrile, it is preferred that the solvent selects dimethyl sulfoxide, two One of methylformamide, dimethyl acetamide, lithium chloride solution, ionic liquid, sodium thiocyanate solution, liquor zinci chloridi or Several mixtures.
5. the preparation method of as-spun fibre according to claim 3 or 4, which is characterized in that
Polyacrylonitrile spinning solution is made by the as-spun fibre using wet spinning process;Wherein, spinneret draft multiple is 0.7 ~1.5 times, preferably 0.75~1.2 times, further preferably 0.8~1.1 times;Or
Polyacrylonitrile spinning solution is made by the as-spun fibre using dry-jet wet spinning method;Wherein, spinneret draft multiple It is 2~12 times, preferably 3~8 times, further preferably 4~6 times.
6. a kind of polyacrylonitrile fibre, which is characterized in that average pore size and core at the surface structure of the polyacrylonitrile fibre The deviation between average pore size at layer structure is within 10%;
Preferably, the tensile strength of the polyacrylonitrile fibre is 900MPa-1.5GPa, preferably 950MPa-1.5GPa;
Preferably, the polyacrylonitrile fibre is prepared by the described in any item as-spun fibres of claims 1 or 2.
7. the preparation method of polyacrylonitrile fibre as claimed in claim 6, which comprises the steps of:
It prepares as-spun fibre: being prepared using the preparation method of the described in any item as-spun fibres of claim 3-5 described nascent Fiber;
Drawing-off processing: in gas medium, drawing-off processing is carried out to the as-spun fibre;
Post-processing: treated that as-spun fibre is post-processed for counter extensioin, obtains polyacrylonitrile fibre;
Preferably, the step of post-processing, comprising: counter extensioin treated as-spun fibre carry out washing process, stretch processing, Oiling treatment, drying process, obtain polyacrylonitrile fibre.
8. the preparation method of polyacrylonitrile fibre according to claim 7, which is characterized in that in the step of drawing-off processing In rapid:
The drawing-off handles the drawing-off processing that is positive;It preferably, is 1.05~3.5 to the drafting multiple that the as-spun fibre applies Times, preferably 1.2~3 times, further preferably 1.5~2 times;And/or
The temperature of the gas medium is not higher than 50 DEG C;The temperature of the gas medium is not less than the vitrifying of the as-spun fibre The solvent-laden cryogenic temperature of institute in temperature, as-spun fibre.
9. a kind of polyacrylonitrile-based carbon fibre, which is characterized in that being averaged at the surface structure of the polyacrylonitrile-based carbon fibre The deviation between average pore size at aperture and core structure is within 10%;
Preferably, the average pore size at the average pore size at the surface structure of the polyacrylonitrile-based carbon fibre and core structure it Between deviation within 5%;
Preferably, the tensile strength of the polyacrylonitrile-based carbon fibre is 7.4-9GPa;
Preferably, the polyacrylonitrile-based carbon fibre is prepared by polyacrylonitrile fibre as claimed in claim 6.
10. the preparation method of polyacrylonitrile-based carbon fibre as claimed in claim 9, which comprises the steps of: to poly- Dralon is heat-treated, and polyacrylonitrile-based carbon fibre is obtained;Wherein, polyacrylonitrile fibre is as claimed in claim 6 Polyacrylonitrile fibre;
Preferably, it is described heat treatment include: the polyacrylonitrile fibre is pre-oxidized, low-temperature carbonization, high temperature cabonization processing; Wherein, the temperature of the pre-oxidation is preferably 185~350 DEG C;The temperature of the low-temperature carbonization processing is preferably 400~850 DEG C; The temperature of the high temperature cabonization is preferably 1200~3000 DEG C.
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