CN110359114A - A kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre and preparation method thereof - Google Patents
A kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre and preparation method thereof Download PDFInfo
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- CN110359114A CN110359114A CN201910718254.XA CN201910718254A CN110359114A CN 110359114 A CN110359114 A CN 110359114A CN 201910718254 A CN201910718254 A CN 201910718254A CN 110359114 A CN110359114 A CN 110359114A
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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
- D01D5/04—Dry spinning methods
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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
- D01D5/06—Wet 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
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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
- D01F9/225—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 from stabilised polyacrylonitriles
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- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The present invention relates to a kind of polyacrylonitrile fibres, polyacrylonitrile-based carbon fibre and preparation method thereof.The technical solution mainly used are as follows: a kind of preparation method of polyacrylonitrile fibre includes the following steps: that polyacrylonitrile spinning solution is extruded into dynamic analysis of spinning through spinneret orifice；The dynamic analysis of spinning obtains as-spun fibre after solidification forming is handled；In gas medium, drawing-off processing is carried out to the as-spun fibre；Treated that as-spun fibre is post-processed for counter extensioin, obtains polyacrylonitrile fibre.Present invention is mainly used for reduce generated wastewater flow rate in polyacrylonitrile fibre and the Preparation of PAN-based Carbon Fibers.
Description
Technical field
The present invention relates to a kind of fibre technology fields, more particularly to a kind of polyacrylonitrile fibre, polyacrylonitrile-radical carbon fiber
Dimension and preparation method thereof.
Background technique
Polyacrylonitrile fibre it is widely used, be both used directly for textile industry, can also be made after Overheating Treatment
For at polyacrylonitrile-based carbon fibre.
When preparing polyacrylonitrile fibre using wet spinning technology or dry-jet wet spinning technique: dynamic analysis of spinning first passes through
Coagulating bath formed coagulated yarn (coagulated yarn is also referred to as as-spun fibre), then to coagulated yarn carry out aftertreatment technology (e.g., wash, stretch,
Oil, dry), so that coagulated yarn is become polyacrylonitrile fibre.But containing a large amount of molten from the coagulated yarn come out in coagulating bath
Agent must be driven off these solvents in aftertreatment technology, to improve fibre property, meet the needs of following process.
The mode that the prior art directlys adopt washing removes solvent contained in coagulated yarn.But invention of the invention
People discovery: using directly washing by the way of by coagulated yarn solvent remove the direct bring consequence of this technology be generate greatly
The waste water of amount, which not only adds production costs, also can cause environmental pollution.
Summary of the invention
In view of this, the present invention provides a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre and preparation method thereof, mainly
Purpose is to reduce generated wastewater flow rate in polyacrylonitrile fibre and the Preparation of PAN-based Carbon Fibers.
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 preparation method of polyacrylonitrile fibre, which is characterized in that including such as
Lower step:
Prepare as-spun fibre: polyacrylonitrile spinning solution is extruded into dynamic analysis of spinning through spinneret orifice；The dynamic analysis of spinning warp
After supersolidification forming processing, as-spun fibre is obtained；
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.
The object of the invention to solve the technical problems also can be used following technical measures and further realize.
Preferably, in the step of drawing-off is handled, the drawing-off handles the drawing-off processing that is positive；Preferably, it is preferred that
In the step of drawing-off is handled, 2-3 grades of drawing-offs processing are carried out to the as-spun fibre；Preferably, it is handled in the drawing-off
The step of in, to the as-spun fibre apply total draft multiple be 1.05~3.5 times, preferably 1.2~3 times, further it is excellent
It is selected as 1.5~2 times.
Preferably, in the step of drawing-off is handled: the temperature of the gas medium is not higher than 50 DEG C, preferably no greater than
25℃；The temperature of the gas medium is solvent-laden molten not less than institute in the glass transition temperature of the as-spun fibre, as-spun fibre
Point.
Preferably, in the step of drawing-off is handled: the gas medium is air, nitrogen, vapor, indifferent gas
The mixed gas of one or more of body, carbon dioxide.
Preferably, in the step of preparing as-spun fibre: the as-spun fibre is integrally in solidification state or gel state；Or it is described
The part of as-spun fibre is in any one of solidification state, gel state, solution state.
Preferably, in described the step of preparing as-spun fibre, using wet spinning process, dry-jet wet spinning method, dry method
As-spun fibre is made in spinning solution by any one of spinning process；
Preferably, when as-spun fibre is made in polyacrylonitrile spinning solution using wet spinning process: the temperature of coagulating bath
It is 0~70 DEG C, preferably 15~65 DEG C；And/or spinneret draft multiple be 0.7~1.5 times, preferably 0.75~1.2 times,
Further preferably 0.8~1.1 times；
Preferably, when as-spun fibre is made in polyacrylonitrile spinning solution using dry-jet wet spinning method: coagulating bath
Temperature is -50~10 DEG C, further preferably -25~4 DEG C, more preferably -18 DEG C~4 DEG C；And/or spinneret draft multiple is 2
~12 times, preferably 3~8 times, further preferably 4~6 times.
Preferably, the ingredient of the coagulating bath includes solvent and non-solvent；Wherein, the mass ratio of the non-solvent and solvent
It is still more preferably 8:2~6:4 for 1:0~3:7, preferably 1:0~4:6, further preferably 9:1~5:5；Preferably,
The non-solvent formic acid, glycerol, ethylene glycol, acetic acid, ethyl alcohol, methanol, chloroform, isobutanol, isoamyl alcohol, butanediol, benzene first
The mixture of one or more of alcohol, carbon tetrachloride, toluene, acetone, water, dioxane.
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 preparation process of polyacrylonitrile fibre, to the fiber apply total draft multiple be 10 times with
It is upper and less than 350 times, further preferably 25 times or more and less than 150 times.
Preferably, the polymer in the polyacrylonitrile spinning solution is polyacrylonitrile homopolymer；Or
Polymer in the polyacrylonitrile spinning solution is polyacrylonitrile copolymer；Or
Polymer in the polyacrylonitrile spinning solution includes the mixed of polyacrylonitrile homopolymer and polyacrylonitrile copolymer
Close object.
On the other hand, the embodiment of the present invention provides a kind of preparation method of polyacrylonitrile-based carbon fibre, including walks as follows
It is rapid:
Polyacrylonitrile fibre is prepared using the preparation method of above-mentioned polyacrylonitrile fibre；
The polyacrylonitrile fibre is heat-treated, polyacrylonitrile-based carbon fibre is obtained.
In another aspect, the embodiment of the present invention also provides a kind of pan based fibers, wherein the pan based fibers
It is prepared by the preparation method of above-mentioned polyacrylonitrile fibre；
Preferably, when in the step of preparing as-spun fibre, when the diameter D of spinneret orifice is 0.045≤D < 0.1mm: described
The diameter of polyacrylonitrile fibre is 4.2~12 μm, the volume density of polyacrylonitrile fibre is 1.186~1.20g/cm3；
When in the step of preparing as-spun fibre, when the diameter D of spinneret orifice is 0.1≤D < 0.3mm: the polyacrylonitrile is fine
The diameter of dimension is 6~13.2 μm, the volume density of polyacrylonitrile fibre is 1.184~1.19g/cm3；
When in the step of preparing as-spun fibre, when the diameter D of spinneret orifice is 0.3≤D≤2mm: the polyacrylonitrile is fine
The diameter of dimension is 7~17 μm, the volume density of polyacrylonitrile fibre is 1.184~1.195g/cm3。
In another aspect, the embodiment of the present invention also provides a kind of polyacrylonitrile-based carbon fibre, wherein the polyacrylonitrile-based carbon
Fiber is prepared by the preparation method of above-mentioned polyacrylonitrile-based carbon fibre；
Preferably, when in the step of preparing as-spun fibre, when the diameter D of spinneret orifice is 0.045≤D < 0.1mm: described
The diameter of polyacrylonitrile-based carbon fibre is 3~7.6 μm, the volume density of polyacrylonitrile-based carbon fibre is 1.84~1.96g/cm3；
When in the step of preparing as-spun fibre, when the diameter D of spinneret orifice is 0.1≤D < 0.3mm: the polyacrylonitrile-radical
The diameter of carbon fiber is 4.5~8.1 μm, the volume density of polyacrylonitrile-based carbon fibre is 1.79~2.0g/cm3；
When in the step of preparing as-spun fibre, when the diameter D of spinneret orifice is 0.3≤D≤2mm: the polyacrylonitrile-radical
The diameter of carbon fiber is 5~10 μm, the volume density of polyacrylonitrile-based carbon fibre is 1.180~1.83g/cm3。
Compared with prior art, polyacrylonitrile fibre of the invention, polyacrylonitrile-based carbon fibre and preparation method thereof be at least
With following the utility model has the advantages that
On the one hand, the preparation method of polyacrylonitrile fibre provided in an embodiment of the present invention, by forming as-spun fibre
After step, before being post-processed to as-spun fibre and (including the steps that washing, stretch, oil, drying process): adding pair
As-spun fibre carries out the step of positive drawing-off processing in gas medium, in this way, can apply tension to as-spun fibre, in nascent fibre
While dimension form strand is elongated, extrusion effect is formed to the solvent contained by strand inside, solvent contained by strand is forced to ooze out
To strand surface, the solvent of exudation forms drop and leaves strand, thus reach the technical effect of partial solvent in removal strand, from
And reduce the wastewater flow rate of subsequent washing process.
Further, the preparation method of polyacrylonitrile fibre provided in an embodiment of the present invention is led to when preparing as-spun fibre
The temperature of control coagulating bath and the composition of coagulation bath are crossed, is also possible to as-spun fibre (partially in gel state) in gel state,
The as-spun fibre of gel state handles phase coordinated with positive drawing-off in this way, and the effect squeezed strand becomes apparent from, and can squeeze out strand
In most of solvent, the wastewater flow rate of significantly less subsequent washing process.
On the other hand, the embodiment of the present invention also provides a kind of preparation method of polyacrylonitrile-based carbon fibre, wherein described poly-
It include the preparation method of above-mentioned polyacrylonitrile fibre in the preparation method of acrylonitrile base carbon fiber, therefore, the present invention is implemented
The preparation method for the polyacrylonitrile-based carbon fibre that example provides also achieves the beneficial effect for reducing wastewater flow rate.
In addition, compared with prior art, the preparation method of polyacrylonitrile fibre provided in an embodiment of the present invention, polyacrylonitrile
The preparation method of base carbon fibre can make the polyacrylonitrile fibre prepared, the diameter of polyacrylonitrile-based carbon fibre smaller, volume density
It is bigger, so as to keep the properity of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre more excellent.
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, with presently preferred embodiments of the present invention, detailed description is as follows below.
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 preferably
Embodiment, to specific embodiment, structure, feature and its effect applied according to the present invention, detailed description is as follows.It is stated under
In bright, what different " embodiment " or " embodiment " referred to is not necessarily the same embodiment.In addition, in one or more embodiments
Special characteristic, structure or feature can be combined by any suitable form.
On the one hand, the embodiment of the present invention provides a kind of preparation method of polyacrylonitrile fibre, includes the following steps:
1) polyacrylonitrile spinning solution is extruded into dynamic analysis of spinning through spinneret orifice；The dynamic analysis of spinning is in solidification forming processing
Afterwards, as-spun fibre is obtained.
Polyacrylonitrile spinning solution in the step refers to: using polyacrylonitrile and polyacrylonitrile solvent as the solution of component.
Here, polyacrylonitrile refers to polyacrylonitrile homopolymer or is with acrylonitrile copolymer as main component and with acrylonitrile
Homopolymer obtains polyacrylonitrile blend as main component with acrylonitrile copolymer as main component.As long as in addition, not
It damages in effective scope of the invention, may include other substances in the spinning solution of polyacrylonitrile.
Here, polyacrylonitrile solvent is the solvent that can dissolve polyacrylonitrile；Preferably dimethyl sulfoxide, dimethyl formyl
The single substances such as amine, dimethyl acetamide, dimethyl sulfoxide/lithium chloride, ionic liquid, sodium thiocyanate solution, liquor zinci chloridi,
It is also possible to above-mentioned substance mixture.
Here, the molecular chain conformation of polyacrylonitrile is not particularly limited, as long as can obtain fiber by spinning technique
The polyacrylonitrile of form.Consider from the mechanical property of polyacrylonitrile fibre, preferably 70,000 or more polyacrylonitrile molecular weight, into
Preferred 100,000 or more the polyacrylonitrile molecular weight of one step.The more big polyacrylonitrile fibre mechanical property obtained of molecular weight is better, but
The dissolubility of macromolecule polyacrylonitrile in a solvent is poor, therefore the upper limit of polyacrylonitrile molecular weight is not particularly limited, only
Want polyacrylonitrile that can be dissolved in solvent, usual polyacrylonitrile is below 1,500,000.Polyacrylonitrile fibre in order to balance
Mechanical property and spinning properties, also can be used macromolecule polyacrylonitrile and small-molecular-weight polyacrylonitrile is cooperatively dissolved in
The spinning solution of polyacrylonitrile is obtained in solvent.
Preferably, the spinning technique refers to that the spinning solution of polyacrylonitrile, which is carried out spinning, to be had in the step
There is the process of fibre morphology strand.The preferred wet spinning process of spinning technique and dry-jet wet spinning method.
Preferably, the polyacrylonitrile fibre form strand formed in spinning technique used in the step can be generally in
Curdled appearance (without elasticity), can be gel state；It can also be and be partially in curdled appearance (e.g., the only Pi Shining of fiber
Solid-state, core can be solution state or gel state), (e.g., the skin of fiber is solidification state or gel state to solution state, and the core of fiber is
Solution state) or gel state (e.g., the skin of fiber be solidification state, core is gel state；For another example, the skin of fiber is the core of gel state, fiber
It is solution state).Preferably selecting spinning process condition makes as-spun fibre generally in gel state.
Preferably, preferably can make the spinning solution of polyacrylonitrile in fiber forming process in the spinning technique of the step
The spinning process condition for undergoing gel state, for example, by using the fiber forming process condition of low temperature coagulating bath.The spinning of polyacrylonitrile
The loss modulus of stoste is greater than storage modulus, and gel state in this refers to that the spinning solution of polyacrylonitrile changes during the spinning process
It is equal to or less than state when storage modulus for its loss modulus, but the spinning solution of entire polyacrylonitrile still has part not have
Generation mutually separates.
In the step, spinning technique can be any one of dry method method, wet spinning, dry-jet wet spinning；It is preferred that
Wet spinning process or dry-jet wet spinning method.
Here, for dry-spinning process: also containing a large amount of solvent when fiber goes out path, i.e. fiber is completely solidifying not yet
Gu when, partial solvent can be removed by this method, then carry out subsequent processing.Using the form of dry spinning, i.e. spinning
Liquid enters in path, but the temperature in path is low temperature, and spinning solution thread forms gel state at this time, can also be subsequently through sky
Gas drawing-off removes solvent.
Preferably, when using wet spinning process or dry-jet wet spinning method in the spinning technique of the step, coagulating bath component
Mainly polyacrylonitrile solvent (solvent of dissolution polyacrylonitrile, abbreviation solvent) and polyacrylonitrile non-solvent (insoluble polypropylene
The solvent of nitrile, abbreviation non-solvent)；Wherein, the mass ratio of non-solvent and solvent is 1:0~3:7, will be above-mentioned using the coagulating bath
The spinning solution of polyacrylonitrile forms fibre morphology.Preferably, the mass ratio of non-solvent and solvent is 1:0~4:6, further excellent
It is selected as 9:1~5:5, is still more preferably 8:2~6:4.Herein, the non-solvent can be single substance, be also possible to
The mixture of different material；Such as it can be formic acid, glycerol, ethylene glycol, acetic acid, ethyl alcohol, methanol, chloroform, isobutanol, isoamyl
The mixture of one or more of alcohol, butanediol, benzyl alcohol, carbon tetrachloride, toluene, acetone, water, dioxane.Coagulating bath
In component in remove solvent and non-solvent, can not also damage the other components of effect of the invention comprising other, exactly solidify
In addition to the solvent and non-solvent listed in bath, there may also be other components.
Preferably, the spinning technique for using wet spinning process or dry-jet wet spinning method, coagulation bath temperature preferably-
50~70 DEG C, and it is higher than the fusing point of coagulation bath composition.Wherein, when spinning technique is wet spinning, coagulation bath temperature is preferably 0
~70 DEG C, further preferably 15~65 DEG C.When spinning technique is dry-jet wet spinning, coagulation bath temperature is preferably set to low
Temperature, specific coagulation bath temperature are preferably -50~10 DEG C, further preferably -25~4 DEG C, more preferably -18~4 DEG C.Solidification
When bath temperature is lower than -50 DEG C, the spinning solution solidification forming of polyacrylonitrile is slow, and energy consumption is high；Coagulation bath temperature is higher than poly- at 70 DEG C
The spinning solution setting rate of acrylonitrile is too fast, is unfavorable for forming the uniform fiber strand silk of structure.Coagulation bath temperature is -18~10
DEG C when be conducive to polyacrylonitrile spinning solution formed gel state so that fiber strand silk structure is uniform, drawability is strong, is conducive to
Obtain the coagulated yarn of high quality.
The setting of the temperature of the composition and coagulating bath of above-mentioned coagulating bath, can avoid fiber that phase occurs in forming process as far as possible
Separation makes as-spun fibre in gel state (be also possible to part in gel state) as far as possible, the as-spun fibre of such gel state with just lead
Processing phase coordinated is stretched, the effect squeezed strand becomes apparent from, and can squeeze out most of solvent in strand, significantly less subsequent
The wastewater flow rate of washing process.
Preferably, if spinneret draft multiple can be 0.7~1.5 times when using wet spinning in the step, preferably
0.75~1.2 times, further preferably 0.8~1.1 times.If spinneret draft multiple can when the step uses dry-jet wet spinning
Think 2~12 times, preferably 3~8 times, further preferably 4~6 times (spinneret draft multiple is too small, and fiber is just saved bit by bit solidifying
Gu fibre property is also bad, there is no drawing-off, and the diameter and CV value of fiber also not control in bath.Spinneret draft multiple
It is excessive, be easy to produce lousiness, influence to continuously generate, in addition, fiber is also difficult to drawing-off again when post-processing).
In this application, term " spinneret draft multiple " to those skilled in the art, refers to: after spinneret,
The velocity ratio of first speed for being actively driven rod and spinning solution thread outflow spinneret orifice.
2) in gas medium, drawing-off processing is carried out to the as-spun fibre.
Preferably, in this step, drawing-off handles the drawing-off processing that is positive.
Preferably, in the step, the drafting multiple that the as-spun fibre applies is 1.05~3.5 times, preferably 1.2~
3 times, further preferably 1.5~2 times.
Preferably, in this step, multistage drafting processing can be carried out to as-spun fibre；Here, being classified main benefit
It exactly can reduce the lousiness amount of high draft generation, increase and squeeze out effect.
Preferably, in this step, the temperature of the gas medium is not higher than 25 DEG C；The temperature of the gas medium is not low
The solvent-laden cryogenic temperature of institute in the glass transition temperature of the as-spun fibre, as-spun fibre.
Preferably, in this step: the gas medium is air, in nitrogen, vapor, inert gas, carbon dioxide
It is any.
3) treated that as-spun fibre is post-processed for counter extensioin, obtains polyacrylonitrile fibre.
The step of post-processing, comprising: counter extensioin treated as-spun fibre carry out washing process, stretch processing, on
Oil processing, drying process, obtain polyacrylonitrile fibre.
Preferably, stretch processing can be the stretch processing in bath, it is also possible to vapor stretch processing or xeothermic stretching
Processing.
Preferably, oiling treatment is to assign a protective layer to fiber sheath, prevents from gluing connection between fiber, reduces electrostatic,
Increase the convergence and fiber separation of fibre bundle, preferably to carrying out oiling treatment after fiber strand silk after stretching in bath.
When increasing draw ratio, molecule is easy along fiber axial direction orientations, and fibre property increases.In polyacrylonitrile fibre
Preparation process in, be 10 times or more and less than 350 times, further preferably 25 to the total draft multiple that the fiber applies
Times or more and less than 150 times (that is, since spinneret to the end wind receive silk when all steps drafting multiple).
To sum up, compared with prior art, the preparation method of polyacrylonitrile fibre provided in an embodiment of the present invention, by shape
At after the step of as-spun fibre, in the step for being post-processed to as-spun fibre and (including washing, stretching, oil, drying process)
Before rapid: the step of carrying out positive drawing-off processing in gas medium to as-spun fibre is added, in this way, can apply to as-spun fibre
Tension forms extrusion effect to the solvent contained by strand inside, forces strand while as-spun fibre form strand is elongated
Contained solvent is exuded to strand surface, and the solvent of exudation forms drop and leaves strand, to reach partial solvent in removal strand
Technical effect, to reduce the wastewater flow rate of subsequent washing process.
On the other hand, the embodiment of the present invention also provides a kind of polyacrylonitrile-based carbon fibre, includes the following steps:
It prepares polyacrylonitrile fibre: polyacrylonitrile fibre is prepared using the preparation method of above-mentioned polyacrylonitrile fibre；
Heat treatment: polyacrylonitrile is heat-treated, polyacrylonitrile-based carbon fibre is obtained.
Heat treatment process in this, as long as polyacrylonitrile fibre can be made to become carbon fiber by heating, without spy
It does not limit, such as can be pre-oxidation process, low-temperature carbonization technique, high temperature cabonization technique.
Preferably, polyacrylonitrile fibre successively obtains carbon fiber by following technique:
Pre-oxidation process, by the carbon fiber precursor fiber of above-mentioned acquisition 185~350 DEG C at a temperature of air in carry out
Pre-oxidation；
Low-temperature carbonization technique carries out fiber obtained in pre-oxidation process at a temperature of 400~850 DEG C in inert atmosphere
Low-temperature carbonization；
High temperature cabonization technique, by the fiber obtained in low-temperature carbonization technique at a temperature of 1200~3000 DEG C in inert atmosphere
It is carbonized.
It, can be by being electrolysed to carbon fiber in order to increase the bond strength of matrix in carbon fiber and fibre reinforced composites
Surface is handled.After electrolysis processing, in order to increase carbon fiber convergence and subsequent service performance, starching can be carried out to carbon fiber
Processing.Sizing agent used in starching processing is selected according to the type of matrix in composite material.
It is described in further detail below by specific experiment embodiment.
Embodiment 1
The present embodiment provides the preparation methods of a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre, specifically include as follows
Step:
1) prepare polyacrylonitrile spinning solution: using dimethyl sulfoxide as solvent, using acrylonitrile and itaconic acid as comonomer,
It is polyacrylonitrile spinning solution by the polyacrylonitrile solution that polymerisation in solution obtains, viscosity average molecular weigh is 140,000, and viscosity is
80Pa.s is (here, the present embodiment and following embodiments are mainly 140,000, viscosity for the poly- of 80Pa.s with the viscosity average molecular weigh used
Illustrate for acrylonitrile spinning solution, but not limited to this, any one polyacryl-nitrile spinning fluid is suitable for the present invention).
2) prepare as-spun fibre: using dry-jet wet spinning method, (wherein, spinneret draft multiple is 6.0, spinneret orifice
Diameter is 0.12mm) prepare as-spun fibre；In this step: the temperature control of coagulating bath is -15 DEG C, and coagulation bath composition is matter
Amount is than the dimethyl sulfoxide and water for 7:3.
3) drawing-off is handled: carrying out drawing-off processing to as-spun fibre in gas medium；Wherein, gas medium is air, right
The drafting multiple that as-spun fibre applies is 3.5 times.
4) post-process: using water-bath counter extensioin, treated that as-spun fibre washed, stretch processing, obtains water-bath fibre
Dimension；Oiling treatment is carried out to water-bath fiber again, densification then is dried to fiber using dryer roll, and in high-temperature water
After carrying out drawing-off in steam, polyacrylonitrile fibre is obtained.
The polyacrylonitrile fibre that fibre number is 0.90dtex is obtained in the preparation process of above-mentioned polyacrylonitrile fibre.
5) it is heat-treated: by the air for the temperature gradient that obtained polyacrylonitrile fibre is 185~350 DEG C in temperature range
In pre-oxidized, obtain pre-oxidized fibers.By obtained pre-oxidized fibers in the nitrogen atmosphere that temperature is 400~850 DEG C
Low-temperature carbonization is carried out, low-temperature carbonization fiber is obtained.By low-temperature carbonization fiber maximum temperature be in 1600 DEG C of nitrogen atmosphere into
Row high temperature cabonization, and electrolysis processing is carried out as electrolyte using ammonium bisulfate solution, and washed, dried, then carry out
Starching processing, obtains polyacrylonitrile-based carbon fibre.
Embodiment 2
The present embodiment provides the preparation methods of a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre；The present embodiment and reality
The difference for applying example 1 is:
In preparing as-spun fibre step: spinneret draft multiple is 2 times；The diameter of spinneret orifice is 0.5mm；Coagulating bath
Temperature be 10 DEG C；Coagulation bath composition is the dimethyl acetamide and water that mass ratio is 6:4；
In drawing-off processing step: gas medium is air, is 2 to the drafting multiple that as-spun fibre applies in gas medium
Times；
The step of other steps are with embodiment 1 is consistent.
Embodiment 3
The present embodiment provides the preparation methods of a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre；The present embodiment and reality
The difference for applying example 1 is:
In preparing as-spun fibre step: spinneret draft multiple is 12 times, and the diameter of spinneret orifice is 0.15mm；Coagulating bath
Temperature is -25 DEG C, and coagulation bath composition is ethyl alcohol；
In drawing-off processing step: gas medium is air, is 3 to the drafting multiple that as-spun fibre applies in gas medium
Times；
The step of other steps are with embodiment 1 is consistent.
Embodiment 4
The present embodiment provides the preparation methods of a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre；The present embodiment and reality
The difference for applying example 1 is:
In the step of preparing as-spun fibre: spinneret draft multiple is 1.2 times, and the diameter of spinneret orifice is 0.1mm, solidification
Bath temperature is 3 DEG C, and the ingredient of coagulating bath is water；
In drawing-off processing step: gas medium is air, and the drafting multiple applied in gas medium to as-spun fibre is
1.5 again.
The step of other steps are with embodiment 1 is consistent.
Embodiment 5
The present embodiment provides the preparation methods of a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre；The present embodiment and reality
The difference for applying example 1 is:
In the step of preparing as-spun fibre: spinneret draft multiple is 8 times, and the diameter of spinneret orifice is 0.2mm；Solidification
Bath temperature is -18 DEG C, and coagulation bath composition is the second alcohol and water that mass ratio is 9:1；
In drawing-off processing step: gas medium is air, the drafting multiple applied in gas medium to as-spun fibre
It is 2.5 times.
The step of other steps are with embodiment 1 is consistent.
Embodiment 6
The present embodiment provides the preparation methods of a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre；The present embodiment and reality
The difference for applying example 1 is:
In the step of preparing as-spun fibre: spinneret draft multiple is 4 times, and the diameter of spinneret orifice is 0.3mm；Solidification
Bath temperature is 1 DEG C, and coagulation bath composition is the isopropanol and dimethylformamide that mass ratio is 5:5；
In drawing-off processing step: gas medium is air, the drafting multiple applied in gas medium to as-spun fibre
It is 1.05 times.
The step of other steps are with embodiment 1 is consistent.
Embodiment 7
The present embodiment provides the preparation methods of a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre；The present embodiment and reality
The difference for applying example 1 is:
In the step of preparing as-spun fibre: using wet spinning technology, spinneret draft multiple is 1.1 times, spinneret orifice
Diameter be 0.045mm；Coagulation bath temperature is 15 DEG C, and coagulation bath composition is the dimethyl sulfoxide and water that mass ratio is 4:6；
In drawing-off processing step: gas medium is nitrogen, the drafting multiple applied in gas medium to as-spun fibre
It is 1.4 times.
The step of other steps are with embodiment 1 is consistent.
Embodiment 8
The present embodiment provides the preparation methods of a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre；The present embodiment and reality
The difference for applying example 1 is:
In the step of preparing as-spun fibre: using wet spinning technology, spinneret draft multiple is 0.8 times, spinneret orifice
Diameter be 0.06mm；Coagulation bath temperature is 65 DEG C, and coagulation bath composition is the dimethyl sulfoxide and water that mass ratio is 6:4；
In drawing-off processing step, gas medium is nitrogen, and the drafting multiple applied in gas medium to as-spun fibre is
1.2 again.
The step of other steps are with embodiment 1 is consistent.
Embodiment 9
The present embodiment provides the preparation methods of a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre；The present embodiment and reality
The difference for applying example 1 is:
In the step of preparing as-spun fibre: using wet spinning technology, spinneret draft multiple is 0.75 times, spinneret
The diameter in hole is 0.07mm；Coagulation bath temperature is 70 DEG C, and coagulation bath composition is the dimethyl sulfoxide and water that mass ratio is 7:3；
In drawing-off processing step: gas medium is carbon dioxide, the drawing-off applied in gas medium to as-spun fibre
Multiple is 1.1 times.
The step of other steps are with embodiment 1 is consistent.
Embodiment 10
The present embodiment provides the preparation methods of a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre；The present embodiment and reality
The difference for applying example 1 is:
In the step of preparing as-spun fibre: spinneret draft multiple is 3 times, and the diameter of spinneret orifice is 1mm；Coagulating bath
Temperature is -50 DEG C, and coagulation bath composition is methanol；
In drawing-off processing step: gas medium is vapor, the drawing-off times applied in gas medium to as-spun fibre
Number is 1.6 times.
The step of other steps are with embodiment 1 is consistent.
Embodiment 11
The present embodiment provides the preparation methods of a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre；The present embodiment and reality
The difference for applying example 1 is:
In the step of preparing as-spun fibre: spinneret draft multiple is 1.5 times, and the diameter of spinneret orifice is 2mm；Coagulating bath
Temperature be -10 DEG C, coagulation bath composition be quality be 4:5:1 dimethyl sulfoxide, water, methanol；
In drawing-off processing step: gas medium is nitrogen, the drafting multiple applied in gas medium to as-spun fibre
It is 1.8 times.
The step of other steps are with embodiment 1 is consistent.
Embodiment 12
The present embodiment provides the preparation methods of a kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre；The present embodiment and reality
The difference for applying example 1 is:
In the step of preparing as-spun fibre: using wet spinning technology, spinneret draft multiple is 0.7 times, spinneret orifice
Diameter be 0.25mm；Coagulation bath temperature is 60 DEG C, and coagulation bath composition is the dimethyl sulfoxide and water that mass ratio is 3:7；
In drawing-off processing step: gas medium is nitrogen, and the drafting multiple applied in gas medium to as-spun fibre is
1.3 again.
The step of other steps are with embodiment 1 is consistent.
Comparative example 1
In preparation process prepared by polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre, not to first in gas medium
Raw fiber carries out drafting process, and the operation of other steps similarly to Example 1 obtains polyacrylonitrile-based carbon fibre.
Comparative example 2
In preparation process prepared by polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre, not to first in gas medium
Raw fiber carries out drafting process, and the operation of other steps similarly to Example 2 obtains polyacrylonitrile-based carbon fibre.
Comparative example 3
In preparation process prepared by polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre, not to first in gas medium
Raw fiber carries out drafting process, and the operation of other steps similarly to Example 3 obtains polyacrylonitrile-based carbon fibre.
Comparative example 4
It is right not in gas medium in preparation process prepared by pan based fibers and polyacrylonitrile-based carbon fibre
As-spun fibre carries out drafting process, and the operation of other steps similarly to Example 4 obtains polyacrylonitrile-based carbon fibre.
Comparative example 5
In preparation process prepared by polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre, not to first in gas medium
Raw fiber carries out drafting process, and the operation of other steps similarly to Example 5 obtains polyacrylonitrile-based carbon fibre.
Comparative example 6
In preparation process prepared by polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre, not to first in gas medium
Raw fiber carries out drafting process, and the operation of other steps similarly to Example 8 obtains polyacrylonitrile-based carbon fibre.
Comparative example 7
In preparation process prepared by polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre, not to first in gas medium
Raw fiber carries out drafting process, and the operation of other steps similarly to Example 9 obtains polyacrylonitrile-based carbon fibre.
Embodiment 1- embodiment 12, the preparation technology parameter of comparative example 1- comparative example 7, wastewater flow rate caused by preparation process
Ginseng is shown in Table 1.
Table 1 is embodiment 1-12, the preparation technology parameter of comparative example 1-7, wastewater flow rate list caused by preparation process
It can be seen from Table 1 that:
(1) polyacrylonitrile fibre provided in an embodiment of the present invention, polyacrylonitrile-based carbon fibre preparation method can reduce
Wastewater flow rate reduces 10% or more.
(2) by the temperature of control coagulating bath and the composition of coagulation bath, make as-spun fibre in gel state, such gel state
As-spun fibre and positive drawing-off handle phase coordinated, to strand squeeze effect become apparent from, the major part in strand can be squeezed out
Solvent, the wastewater flow rate of significantly less subsequent washing process.
Embodiment 1- embodiment 12, comparative example 1- comparative example 7 preparation technology parameter, prepare the parameter of product referring to table
Shown in 2.
Table 2 is embodiment 1-12, the preparation technology parameter of comparative example 1-7, prepares the parameter list of product
As can be seen from Table 2:
(1) compared with the prior art, can be made using the preparation method of polyacrylonitrile fibre provided in an embodiment of the present invention
Polyacrylonitrile fibre fine-denier is obtained, the diameter of polyacrylonitrile fibre can be reduced, increase the volume density of polyacrylonitrile fibre.
It (2) compared with the prior art, can using the preparation method of polyacrylonitrile-based carbon fibre provided in an embodiment of the present invention
So that polyacrylonitrile-based carbon fibre fine-denier, reduces the diameter of polyacrylonitrile-based carbon fibre, increases polyacrylonitrile-based carbon fibre
Volume density.
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 (12)
1. a kind of preparation method of polyacrylonitrile fibre, which comprises the steps of:
Prepare as-spun fibre: polyacrylonitrile spinning solution is extruded into dynamic analysis of spinning through spinneret orifice；The dynamic analysis of spinning is by solidifying
Gu obtaining as-spun fibre after forming processing；
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.
2. the preparation method of polyacrylonitrile fibre according to claim 1, 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；
Preferably, in the step of drawing-off is handled, 2-3 grades of drawing-off processing are carried out to the as-spun fibre；
It preferably, is 1.05~3.5 to the total draft multiple that the as-spun fibre applies in the step of drawing-off is handled
Times, preferably 1.2~3 times, further preferably 1.5~2 times.
3. the preparation method of polyacrylonitrile fibre according to claim 1, which is characterized in that in the step of drawing-off processing
In rapid:
The temperature of the gas medium is not higher than 50 DEG C, it is preferred that the temperature of the gas medium is not higher than 25 DEG C；
The temperature of the gas medium is solvent-laden molten not less than institute in the glass transition temperature of the as-spun fibre, as-spun fibre
Point.
4. the preparation method of polyacrylonitrile fibre according to claim 1, which is characterized in that in the step of drawing-off processing
In rapid:
The gas medium is the mixed gas of one or more of air, nitrogen, vapor, inert gas, carbon dioxide.
5. the preparation method of polyacrylonitrile fibre described in -4 according to claim 1, which is characterized in that in the nascent fibre of the preparation
In the step of dimension:
The as-spun fibre is integrally in solidification state or gel state；Or
The part of the as-spun fibre is in any one of solidification state, gel state, solution state.
6. the preparation method of polyacrylonitrile fibre according to claim 1, which is characterized in that prepare as-spun fibre described
The step of in, polyacrylonitrile is spun using any spinning process in wet spinning process, dry-jet wet spinning method, dry spinning
As-spun fibre is made in silk stock solution；
Wherein, when as-spun fibre is made in polyacrylonitrile spinning solution using wet spinning process:
The temperature of coagulating bath is 0~70 DEG C, preferably 15~65 DEG C；And/or spinneret draft multiple is 0.7~1.5 times, preferably
It is 0.75~1.2 times, further preferably 0.8~1.1 times；
Wherein, when as-spun fibre is made in polyacrylonitrile spinning solution using dry-jet wet spinning method:
The temperature of coagulating bath is -50~10 DEG C, further preferably -25~4 DEG C, more preferably -18 DEG C~4 DEG C；And/or spinning head
Drafting multiple is 2~12 times, preferably 3~8 times, further preferably 4~6 times.
7. the preparation method of polyacrylonitrile fibre according to claim 6, which is characterized in that
The ingredient of the coagulating bath includes solvent and non-solvent；Wherein, the mass ratio of the non-solvent and solvent is 1:0~3:7,
Preferably 1:0~4:6, further preferably 9:1~5:5 are still more preferably 8:2~6:4；
Preferably, the non-solvent formic acid, glycerol, ethylene glycol, acetic acid, ethyl alcohol, methanol, chloroform, isobutanol, isoamyl alcohol,
The mixture of one or more of butanediol, benzyl alcohol, carbon tetrachloride, toluene, acetone, water, dioxane；
Preferably, the solvent is the solvent that can dissolve polyacrylonitrile；It is further preferred that the solvent selects dimethyl sub-
Sulfone, dimethylformamide, dimethyl acetamide, lithium chloride solution, ionic liquid, sodium thiocyanate solution, in liquor zinci chloridi
One or more of mixtures.
8. the preparation method of polyacrylonitrile fibre according to claim 1-7, which is characterized in that the post-processing
The step of, comprising: counter extensioin treated as-spun fibre carries out washing process, stretch processing, oiling treatment, drying process, obtains
To polyacrylonitrile fibre；
Preferably, in the preparation process of polyacrylonitrile fibre: to the fiber apply total draft multiple be 10 times or more and
Less than 350 times, further preferably 25 times or more and less than 150 times.
9. the preparation method of polyacrylonitrile fibre according to claim 1-8, which is characterized in that
Polymer in the polyacrylonitrile spinning solution is polyacrylonitrile homopolymer；Or
Polymer in the polyacrylonitrile spinning solution is polyacrylonitrile copolymer；Or
Polymer in the polyacrylonitrile spinning solution includes the mixture of polyacrylonitrile homopolymer and polyacrylonitrile copolymer.
10. a kind of preparation method of polyacrylonitrile-based carbon fibre, which comprises the steps of:
Polyacrylonitrile fibre is prepared using the preparation method of the described in any item polyacrylonitrile fibres of claim 1-9；
The polyacrylonitrile fibre is heat-treated, polyacrylonitrile-based carbon fibre is obtained.
11. a kind of pan based fibers, which is characterized in that the pan based fibers are by any one of claim 1-9 institute
The preparation method for the polyacrylonitrile fibre stated is prepared；
Preferably, when in the step of preparing as-spun fibre, when the diameter D of spinneret orifice is 0.045≤D < 0.1mm: described poly- third
The diameter of alkene nitrile fiber is 4.2~12 μm, the volume density of polyacrylonitrile fibre is 1.186~1.20g/cm3；
When in the step of preparing as-spun fibre, when the diameter D of spinneret orifice is 0.1≤D < 0.3mm: the polyacrylonitrile fibre
Diameter is 6~13.2 μm, the volume density of polyacrylonitrile fibre is 1.184~1.19g/cm3；
When in the step of preparing as-spun fibre, when the diameter D of spinneret orifice is 0.3≤D≤2mm: the polyacrylonitrile fibre
Diameter is 7~17 μm, the volume density of polyacrylonitrile fibre is 1.184~1.195g/cm3。
12. a kind of polyacrylonitrile-based carbon fibre, which is characterized in that the polyacrylonitrile-based carbon fibre is by described in any one of claim 10
The preparation method of polyacrylonitrile-based carbon fibre is prepared；
Preferably, when in the step of preparing as-spun fibre, when the diameter D of spinneret orifice is 0.045≤D < 0.1mm: described poly- third
The diameter of alkene itrile group carbon fiber is 3~7.6 μm, the volume density of polyacrylonitrile-based carbon fibre is 1.84~1.96g/cm3；
When in the step of preparing as-spun fibre, when the diameter D of spinneret orifice is 0.1≤D < 0.3mm: the polyacrylonitrile-radical carbon fiber
The diameter of dimension is 4.5~8.1 μm, the volume density of polyacrylonitrile-based carbon fibre is 1.79~2.0g/cm3；
When in the step of preparing as-spun fibre, when the diameter D of spinneret orifice is 0.3≤D≤2mm: the polyacrylonitrile-radical carbon fiber
The diameter of dimension is 5~10 μm, the volume density of polyacrylonitrile-based carbon fibre is 1.180~1.83g/cm3。
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| CN112899807A (en) * | 2021-01-21 | 2021-06-04 | 中国科学院山西煤炭化学研究所 | High-strength, high-modulus and high-toughness polyacrylonitrile fiber and preparation method thereof |
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