CN102953152B - Preparation method for polyacrylonitrile-based carbon fiber - Google Patents
Preparation method for polyacrylonitrile-based carbon fiber Download PDFInfo
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Abstract
The invention provides a preparation method for a polyacrylonitrile-based carbon fiber. The third monomer of a protofilament spinning raw material, i.e., polyacrylonitrile resin, is itaconic acid; a spinning solution is prepared from the resin by using DMSO or DMAc, and spinning and solidification are carried out so as to prepare a nascent fiber. The nascent fiber successively undergoes the following procedures: water bath drafting in an aqueous solution of a spinning solvent; drip washing with deionized water; dipping in a buffer solution containing acid A and salt B, wherein A is sulfuric acid, hydrochloric acid or nitric acid, and B is a sodium salt or a sylvite of A; water bath drafting in pure water; dipping in an acidic aqueous solution; and hot bath rinsing with deionized water until rinsing liquid is neutral. A carbon fiber protofilament is prepared by subjecting the nascent fiber to post-processing procedures like oiling and dry densification. The protofilament undergoes pre-oxidation in an aerobic atmosphere under the condition of drafting and then undergoes carbonization in an anoxic atmosphere under the condition of drafting so as to obtain a finished product of the polyacrylonitrile-based carbon fiber.
Description
Technical field
The present invention relates to the method for manufacturing polyacrylonitrile-based carbon fibre, the preparing raw material polyacrylonitrile tree of the precursor of carbon fiber
Fat adopts furoate clothing for the 3rd comonomer, and precursor is prepared by solution spinning processes.
Background technology
Carbon fiber has excellent mechanical property, and its high specific strength and specific modulus other materials hardly match, as
A kind of reinforcing material, it is widely used in the field such as manufacture of space flight, airborne vehicle and sports equipment.Carbon fiber is generally by can
Precursor made by carbonization material is obtained Jing pre-oxidation and after being carbonized, because polyacrylonitrile resin has higher carbonization yield, because
This polyacrylonitrile fibre is ideal carbon fibre precursor, and obtained carbon fiber is referred to as polyacrylonitrile-based carbon fibre.
The polyacrylonitrile-based carbon fibre of function admirable is obtained, the purification of precursor is most important, and especially metal impurities are contained
The requirement of amount is higher, such as alkali and alkaline earth metal ions, and they can promote when precursor such as is pre-oxidized, is carbonized at the high-temperature process
CO、CO2Effusion Deng gas in carbon fiber so that be internally formed cavity blemish.If with ash to measure precursor in metal impurities contain
Amount, when ash is less than 0.1 ‰, precursor is generally considered to be High Purity, and thus obtained carbon fiber is by with higher product
Matter.
Metal class impurity in polyacrylonitrile base carbon fiber precursors is essentially from polymer raw, polymerization initiation system and gathers
Conjunction or the solvent of spinning.For metal impurities remove can precursor manufacture last handling process, precursor make after or precursor Jing
Link is carried out using the means of washing after pre-oxidation etc., and prior art is typically first washed with acidic aqueous solution, then is spent
Ionized water is rinsed.United States Patent (USP) US 3,413,094, US 4,113,847, US 4,507,272 describe respectively therein
Portion of techniques,《The pickling of PAN bases fibre carbon fiber precursor and the discussion of ion diffusion mechanism》【《Donghua University's journal (natural section
Learn version)》06 phase in 1993】One text is then washed to PAN as-spun fibres, finished fiber and pre-oxidized fibers, wash temperature, acid
The factors such as liquid concentration, time, stirring and fiber hole have made detailed elaboration for the relation etc. of clean result.It is industrial at present
Just complete the purification roguing to precursor generally before pre-oxidation to process, because metal impurities can be to pre-oxidation in pre-oxidation
The structure of silk is damaged.
As manufacture with common acrylon, the spinning material polyacrylonitrile resin of polyacrylonitrile base carbon fiber precursors not third
A kind of homopolymer of monomer of alkene nitrile polymerization, it must the second comonomer containing 2～5wt% or so, it is conventional as acrylic acid methyl ester.,
Ethyl acrylate, methyl methacrylate, ethyl methacrylate or vinylacetate etc..The presence of second comonomer can destroy poly-
The regularity of acrylonitrile macromole, reduces intermolecular active force so that the drawing-off of as-spun fibre can be smoothed out.Additionally, it
The also Third monomer containing 0.5～2.0wt%, the most frequently used for itaconic acid, the presence in itaconic acid can change polyacrylonitrile pre-
Thermal cyclization reaction behavior during oxidation, reduces oxidation reaction initial temperature and peak temperature, makes oxidation reaction heat release gentle, Wen Feng
Wider, oxidizing process carries out more thorough, and this is conducive to improving the mechanical performance of carbon fiber.
Except NaSCN, ZnCl2And HNO3Deng inorganic salt or aqueous acid as spin solvent beyond, current polyacrylonitrile carbon
Fiber precursor is also more using dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and dimethyl acetylamide (DMAC) etc.
Organic solvent is manufactured for spin solvent with solution spinning processes, and the industrial applications of wherein DMSO and DMAC are more universal.It is existing
The purge process for having precursor in technology mainly includes that acid solution is washed and rinses two steps, and fiber is first soaked with acidic aqueous solution
Stain is washed and fiber is rinsed to neutrality with the metal impurities in clean fiber, then deionized water.It is generally acknowledged that in as-spun fibre
Washing is carried out before unfinished drawing-off and has preferable effect, because now fiber still locates gel state, structure is more loose, it is fine
Metal ion inside dimension easily spreads to cleaning mixture.This washing methods is for the effect for removing metal impurities in fiber very
Ideal, but can bring unfavorable to the drawing-off of fiber.This be due to metal impurities thoroughly clean after, polyacrylonitrile macromolecular chain underpants
Health acid unit is carboxylic acid by the form transformation of carboxylate.It is known that the hydrogen atom on carboxylic acid is presented positive charge because electronics deviates,
Its meeting nitrogen-atoms big with electronegativity in acrylonitrile unit in strand forms hydrogen bond.This hydrogen bond may be present in same macromole
Moiety segments cyclization is made in chain, can exist in is crosslinked the moiety segments of adjacent macromole between different macromole.Due to hydrogen
The adhesion of key is much larger than general intermolecular model Dehua gravitation, and this will cause fiber polymer macromolecule in drawing-off to be difficult to
It is extended and stretches, and the desired result of drawing of fiber is all of polymer macromolecule is straightened and is obtained in the presence of external force
Obtain the higher degree of orientation.Experiment shows, under the premise of draft ratio and other process conditions identicals, the as-spun fibre Jing after pickling
Drawing-off can become more difficult, the tensile strength of precursor product is also presented downward trend, while extension at break is in rising trend.
Generally single fiber extension at break rises about 5% or so, and the lower reduction of broken filament intensity then becomes apparent from, general left up to 15%
The right side, this can undoubtedly have a strong impact on the mechanical performance of carbon fiber finished product.And as-spun fibre completes to be washed then purification after drawing-off again
Effect is preferable not to the utmost, because now fibre structure is more closely, is unfavorable for that metal ion spreads to cleaning mixture.Particularly alkaline earth
The ionization constant of metallic element is relatively low, is difficult to pass through with the alkaline-earth metal ions that carboxylate form is present in Fibrous depth
Pickling is removed, even if reinforcing washing process condition, under normal circumstances ash is still difficult to reach less than 0.1wt ‰ in precursor product
Level.So far, the purification of the above-mentioned precursor of prior art not yet effectively solving and mechanical degradation this contradiction.
The content of the invention
The invention provides a kind of method for preparing polyacrylonitrile-based carbon fibre, the spinning material of carbon fibre precursor is employing
Furoate clothing is the polyacrylonitrile resin of the 3rd comonomer, and precursor adopts DMSO or DMAC for the solution spinning processes of spin solvent
Prepared.The technical problem to be solved is the purpose that precursor reaches purification by washing, while protofilament is disconnected
Resistance to spalling is unaffected, so as to obtain the carbon fiber product of good mechanical performance, to make up the defect of prior art presence.
The following is the present invention and solve the specific technical scheme of above-mentioned technical problem：
A kind of method for preparing polyacrylonitrile-based carbon fibre, the spinning material polyacrylonitrile resin of carbon fibre precursor is three kinds
The copolymer of monomer, the first monomer is acrylonitrile；Second comonomer takes from acrylic acid methyl ester., ethyl acrylate, methyl methacrylate
One kind in ester, ethyl methacrylate or vinylacetate；Third monomer is furoate clothing.Third monomer in polyacrylonitrile resin
Content be 0.5～2.0wt%, and second and Third monomer total content be 1.0～7.0wt%.
The method is comprised the following steps successively：
1) polyacrylonitrile resin is configured to spinning solution with DMSO or DMAC as spin solvent, with concentration as 30～50wt%
The aqueous solution of spin solvent be that coagulating bath is obtained as-spun fibre using solution spinning processes Jing spray webbing and solidification forming；
2) as-spun fibre carries out water-bath drawing-off, bath temperature in the aqueous solution of the spin solvent that concentration is 20～30wt%
85～100 DEG C are controlled to, drafting multiple is controlled to 3.5～5.0；
3) as-spun fibre deionized water drip washing, water temperature is controlled to 45～60 DEG C, and drip washing time control is 2～20min；
4) as-spun fibre is placed in the buffer solution containing acid A and salt B and impregnates, and A is nitric acid, sulphuric acid or hydrochloric acid, and B is A's
Sodium salt or potassium salt, the pH value of buffer solution is 2.0～4.0, and the concentration of sodium ion or potassium ion is 200～800mg/L, is buffered molten
The temperature control of liquid is 45～60 DEG C, and with weight ratio meter, bath raio is controlled to as-spun fibre: buffer solution=1: (15～25), leaching
Stain time control is 2～10min；
5) as-spun fibre carries out water-bath drawing-off in pure water, and bath temperature is controlled to 95～100 DEG C, and drafting multiple is controlled to
1.3～2.0；
6) as-spun fibre is placed in acidic aqueous solution and impregnates, and acid adopts nitric acid, sulphuric acid or hydrochloric acid, the pH value of acidic aqueous solution
For 3.0～5.0, temperature control is 45～60 DEG C, and with weight ratio meter, bath raio is controlled to as-spun fibre: solution=1: (15～25),
Dip time is controlled to 2～8min；
7) as-spun fibre temperature is that 90～100 DEG C of deionized water carries out hot bath rinsing, until rinsing liquid is in neutrality；
8) the post-treated process of as-spun fibre is obtained carbon fibre precursor, and last handling process includes oiling and compacting by drying；
9) carbon fibre precursor is pre-oxidized in the state of drawing-off is imposed in having oxygen atmosphere, obtains preoxided thread；
10) preoxided thread is carbonized in an oxygen-free atmosphere in the state of drawing-off is imposed, and obtains polyacrylonitrile-based carbon fine
Dimension finished product.
Above-mentioned steps 4) described in A be preferably nitric acid, B is preferably sodium nitrate；The pH value of buffer solution is preferably 2.5～
3.5；The concentration of sodium ion or potassium ion is preferably 300～500mg/L；The temperature of buffer solution is preferably 45～55 DEG C；Bath raio
Preferably it is controlled to as-spun fibre: buffer solution=1: (18～23)；Dip time is preferably controlled to 4～8min.
Above-mentioned steps 6) described in the pH value of acidic aqueous solution be preferably 3.5～4.5；The temperature of acidic aqueous solution is preferably controlled
It is made as 50～55 DEG C；Bath raio is preferably controlled to as-spun fibre: solution=1: (18～23)；Dip time is preferably controlled to 3～
5min。
As-spun fibre weight can again be pressed in spinning solution according to the spinning solution extrusion capacity of spinning part and gathered in above-mentioned bath raio
The pure calculating of acrylonitrile resin content.
Same as the prior art, the molecular weight of above-mentioned polyacrylonitrile resin is generally 50000～200000；Above-mentioned steps 1)
Described polyacrylonitrile resin is preferably configured to spinning solution by spin solvent of DMSO, is 30～50wt%'s preferably with concentration
The aqueous solution of DMSO is that coagulating bath is obtained as-spun fibre using solution spinning processes Jing spray webbing and solidification forming；Gather in spinning solution
Acrylonitrile resin content general control is 18～25wt%.
Above-mentioned steps 9) precursor pre-oxidation can typically divide three sections and complete, and first paragraph oxidizing temperature is 210～222 DEG C,
Oxidization time is 20～24min, and drafting multiple is 0～5；Second segment oxidizing temperature be 235～245 DEG C, oxidization time be 20～
24min, drafting multiple is -1～1；3rd section of oxidizing temperature is 255～265 DEG C, and oxidization time is 20～24min, drafting multiple
For -1～1；Step 9) described in the oxygen atmosphere that has be usually air.
Above-mentioned steps 10) described in preoxided thread further carbonization can typically be divided to two sections and complete, first paragraph carburizing temperature
For 350～700 DEG C, carbonization time is 1～2min, and drafting multiple is 3～5 times；Second segment carburizing temperature is 800～1350 DEG C,
Carbonization time is 1～2min, and drafting multiple is -2～0；Step 10) described in oxygen-free atmosphere be usually nitrogen.
When the essence of the present invention is that as-spun fibre carries out washing removal metal impurities in precursor preparation process, by cleaning mixture
The acid solution typically adopted by prior art is changed to a kind of buffer solution containing mineral acid and its corresponding sodium salt or potassium salt.
Washing step is located at before drawing-off, after the buffered solution impregnation washing of as-spun fibre, the metal being free in fiber between macromole
Impurity is washed to remove under the action of an acid, former with the alkaline-earth metal on the furoate clothing unit of carboxylate form presence in macromole
It is sub then be buffered the sodium ion in solution or potassium ion and replace, become sodium salt or potassium salt, and it is not converted into carboxylic acid.As-spun fibre Jing
Drawing-off is carried out immediately after buffer solution dipping washing, due to hydrogen atom and acrylonitrile unit on the hydroxy-acid group of furoate clothing unit
Nitrogen-atoms form hydrogen bond and be avoided by, the macromole curled at random can successfully be straightened orientation in drawing-off.
As-spun fibre completes after drawing-off again to be cleaned sodium ion or potassium ion with acid solution, and then again deionized water is entered
Row rinsing.Because sodium ion or potassium ion have higher ionization constant, complete the as-spun fibre Jing of drawing-off pickling again and
It is entirely capable of reaching the clean purpose of the sodium ion of bringing in buffer solution or potassium ion after deionized water rinsing.Inventor is by testing
Data are confirmed, and process conditions of the as-spun fibre after drawing-off is completed as described in technical solution of the present invention carry out pickling and drift
Wash, the ash of precursor product substantially can be less than 0.1 ‰.
The acid selected in buffer solution is conventional during prior art pickling, as long as sodium salt or potassium salt have in theory good
Water solublity and easily ionization decomposer, but to make rinsing process more easy to control, acid preferably takes both and has identical acid with salt
Root.
Although the present invention is spin solvent only with DMSO or DMAC, those skilled in the art is not difficult to deduce, other
The conventional organic solvent such as DMF of manufacture polyacrylonitrile fibre is applied equally to the technical program.
Compared with prior art the present invention achieves substantial progress, and protofilament has reached removal by the way that washing is satisfactory
The purpose of metal impurities, purification effect is very good.And the drawing-off of fiber then can be smooth, the broken filament of precursor
Intensity is relative can to improve 10～20% or so, and single fiber extension at break can reduce by 5～10% or so, so as to the machinery of carbon fiber product
Performance is significantly improved.
Below by specific embodiment, the invention will be further described.Due to the washing in precursor preparation process
Process is the main distinguishing feature of the present invention, the spinning material of precursor, other spinning and aftertreatment technology, and further pre-
The process such as oxidation and carbonization is essentially identical with prior art, therefore embodiment and comparative example will be focused on when prepared by precursor
Washing process and draft process condition are enumerated, and correspondingly show the testing performance index of the washing of reflection precursor and drawing-off effect
The ash of data, such as precursor, broken filament intensity and extension at break, and carbon fiber product correlation associated therewith refers to
Mark, the such as tensile strength of carbon fiber.
In embodiment and comparative example, precursor broken filament intensity and extension at break press GB/T 14335-2008 measure,
The tensile strength of carbon fiber, stretch moduluses are determined by GB/T3362-2005, and the assay method of precursor ash sees below：
The sample (quality is m, is accurate to 0.0001g) of 4g or so is taken, 800 DEG C of temperature calcinations of Jing is placed in constant weight (quality
For m0) porcelain crucible in, the crucible that will be equipped with sample is placed on electric furnace 10～30min of heating, burns to sample and is ashed without black smoke.In
In cooling a moment on electric furnace, in placing into 800 DEG C of high temperature resistance furnace, calcination 2hr is allowed to be ashed, and after taking out from high temperature furnace, moves
Enter and be cooled in exsiccator room temperature, weighing, (quality is m1)。
It is calculated as follows ash：
Specific embodiment
Embodiment and comparative example precursor prepare the spinning material polyacrylonitrile resin for adopting and pass through aqueous suspension polymerization technique
It is obtained, second, third comonomer in addition to acrylonitrile is respectively acrylic acid methyl ester. and itaconic acid, and the weight ratio of three is 97: 2
: 1, the molecular weight of acrylonitrile resin is 90000.The ash for measuring polyacrylonitrile resin raw material is 1.62 ‰.
First, the preparation of carbon fibre precursor：
【Embodiment 1～10】
1) adopt DMSO that polyacrylonitrile resin is configured to into spinning solution for solvent, polyacrylonitrile resin contains in spinning solution
Measure as 18～25wt%.With the DMSO aqueous solutions of 30～50wt% as coagulating bath is using solution spinning processes Jing spray webbing and is frozen into
Shape is obtained as-spun fibre；
2) as-spun fibre carries out water-bath drawing-off in the DMSO aqueous solutions of 20～30wt%, the bath temperature of each embodiment and
Drafting multiple is shown in Table 1, and this step is defined as into front draft in table；
3) as-spun fibre deionized water drip washing, water temperature is controlled to 45～60 DEG C, and drip washing time control is 2～20min；
4) as-spun fibre is placed in the buffer solution containing acid A and salt B and impregnates, and each embodiment buffer solution is constituted and pH
The control data of value, the temperature of buffer solution, bath raio and dip time etc. is shown in Table 2 and 3；
5) as-spun fibre carries out the control data of water-bath drawing-off, each embodiment bath temperature and drafting multiple in pure water and sees
Table 1, first break draft is defined as in table by this step；
6) as-spun fibre is placed in acidic aqueous solution and impregnates, acid that each embodiment acidic aqueous solution is adopted, pH value and temperature,
The control data of bath raio, dip time etc. is shown in Table 4；
7) as-spun fibre temperature is that 90～100 DEG C of deionized water carries out hot bath rinsing, until rinsing liquid is in neutrality；
8) as-spun fibre Jing oils and the last handling process such as compacting by drying, obtains the polyacrylonitrile that fiber number is 1.22dtex
Base carbon fiber protofilament.
【Embodiment 11～12】
1) adopt DMAC that polyacrylonitrile resin is configured to into spinning solution for solvent, polyacrylonitrile resin contains in spinning solution
Measure as 18～25wt%.With the DMAC aqueous solutions of 30～50wt% as coagulating bath is using solution spinning processes Jing spray webbing and is frozen into
Shape is obtained as-spun fibre；
2)～8) identical with embodiment 1～10.
【Comparative example 1～4】
1)～3) identical with embodiment 1～10, each comparative example step 2) bath temperature and drafting multiple be shown in Table 1；
4) as-spun fibre is placed in acidic aqueous solution and impregnates, acid that each comparative example acidic aqueous solution is adopted, pH value, temperature,
The control data of bath raio and dip time etc. is shown in Table 2 and 3；
5) as-spun fibre temperature is that 90～100 DEG C of deionized water carries out hot bath rinsing, to rinsing liquid in neutrality；
6) as-spun fibre carries out the control data of water-bath drawing-off, each comparative example bath temperature and drafting multiple in pure water and sees
Table 1, first break draft is defined as in table by this step；
7) as-spun fibre Jing oils and the last handling process such as compacting by drying, obtains the polyacrylonitrile that fiber number is 1.22dtex
Base carbon fiber protofilament.
Ash, broken filament intensity and the extension at break of the precursor that each embodiment and comparative example are obtained are tested, is as a result seen
Table 5.
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
2nd, carbon fiber is prepared by precursor：
【Embodiment 13～20, comparative example 5～6】
The part precursor that selection above-described embodiment 1～12 and comparative example 1～4 are obtained further prepares carbon fiber, selection
Precursor is shown in Table listed by 6.
Precursor elder generation Jing pre-oxidizes to obtain preoxided thread.Pre-oxidation is carried out in atmosphere, is divided three sections and is completed, first paragraph oxidizing temperature
For 210～222 DEG C, oxidization time is 20～24min, and drafting multiple is 0～5；Second segment oxidizing temperature is 235～245 DEG C, oxygen
The change time is 20～24min, and drafting multiple is -1～1；3rd section of oxidizing temperature is 255～265 DEG C, oxidization time is 20～
24min, drafting multiple is -1～1；
Preoxided thread is further carbonized in nitrogen, and carbonization be divided to two sections to complete, first paragraph carburizing temperature for 350～
700 DEG C, carbonization time is 1～2min, and drafting multiple is 3～5 times；Second segment carburizing temperature is 800～1350 DEG C, carbonization time
For 1～2min, drafting multiple is -2～0.
Then polyacrylonitrile-based carbon fibre product is obtained, its specification is：12k, 7 μm of monofilament average diameter.
The tensile strength and stretch moduluses of the carbon fiber that testing example 13～20, comparative example 5～6 are obtained, the results are shown in Table
6。
Table 6.
Claims (18)
1. a kind of method for preparing polyacrylonitrile-based carbon fibre, the spinning material polyacrylonitrile resin of carbon fibre precursor is three kinds of lists
The copolymer of body, the first monomer is acrylonitrile；Second comonomer take from acrylic acid methyl ester., ethyl acrylate, methyl methacrylate,
One kind in ethyl methacrylate or vinylacetate；Third monomer is furoate clothing, Third monomer in polyacrylonitrile resin
Content be 0.5～2.0wt%, and second and Third monomer total content be 1.0～7.0wt%, it is characterised in that the preparation side
Method is comprised the following steps successively：
1) polyacrylonitrile resin is configured to spinning solution with DMSO or DMAC as spin solvent, with the spinning that concentration is 30～50wt%
The aqueous solution of silk solvent is that coagulating bath is obtained as-spun fibre using solution spinning processes Jing spray webbing and solidification forming；
2) as-spun fibre carries out water-bath drawing-off, bath temperature control in the aqueous solution of the spin solvent that concentration is 20～30wt%
For 85～100 DEG C, drafting multiple is controlled to 3.5～5.0；
3) as-spun fibre deionized water drip washing, water temperature is controlled to 45～60 DEG C, and drip washing time control is 2～20min；
4) as-spun fibre is placed in the buffer solution containing acid A and salt B and impregnates, and A is nitric acid, sulphuric acid or hydrochloric acid, and B is the sodium salt of A
Or potassium salt, the pH value of buffer solution is 2.0～4.0, and the concentration of sodium ion or potassium ion is 200～800mg/L, buffer solution
Temperature control is 45～60 DEG C, and with weight ratio meter, bath raio is controlled to as-spun fibre: buffer solution=1: (15～25), during dipping
Between be controlled to 2～10min；
5) as-spun fibre carries out water-bath drawing-off in pure water, and bath temperature is controlled to 95～100 DEG C, and drafting multiple is controlled to 1.3
～2.0；
6) as-spun fibre is placed in acidic aqueous solution and impregnates, and acid is using nitric acid, sulphuric acid or hydrochloric acid, the pH value of acidic aqueous solution
3.0～5.0, temperature control is 45～60 DEG C, and with weight ratio meter, bath raio is controlled to as-spun fibre: solution=1: (15～25), leaching
Stain time control is 2～8min；
7) as-spun fibre temperature is that 90～100 DEG C of deionized water carries out hot bath rinsing, until rinsing liquid is in neutrality；
8) the post-treated process of as-spun fibre is obtained carbon fibre precursor, and last handling process includes oiling and compacting by drying；
9) carbon fibre precursor is pre-oxidized in the state of drawing-off is imposed in having oxygen atmosphere, obtains preoxided thread；
10) preoxided thread is carbonized in an oxygen-free atmosphere in the state of drawing-off is imposed, obtain polyacrylonitrile-based carbon fibre into
Product.
2. the method for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 4) described in A be
Nitric acid, B is sodium nitrate.
3. the method for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 4) described in it is slow
The pH value for rushing solution is 2.5～3.5.
4. the method for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 4) described in sodium
The concentration of ion or potassium ion is 300～500mg/L.
5. the method for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 4) described in it is slow
The temperature for rushing solution is 45～55 DEG C.
6. the method for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 4) described in bath
Than being controlled to as-spun fibre: buffer solution=1: (18～23).
7. the method for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 4) described in leaching
Stain time control is 4～8min.
8. the method for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 6) described in acid
Property aqueous solution pH value be 3.5～4.5.
9. the method for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 6) described in acid
Property aqueous solution temperature control be 50～55 DEG C.
10. the method for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 6) described in bath
Than being controlled to as-spun fibre: solution=1: (18～23).
11. methods for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 6) described in leaching
Stain time control is 3～5min.
12. methods for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that described polyacrylonitrile
The molecular weight of resin is 50000～200000.
13. methods for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 1) described in it is poly-
Acrylonitrile resin is configured to spinning solution by spin solvent of DMSO, and the aqueous solution with the DMSO that concentration is 30～50wt% is solidifying
Gu bath is obtained as-spun fibre using solution spinning processes Jing spray webbing and solidification forming.
14. methods for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 1) described in spinning
Polyacrylonitrile resin content is 18～25wt% in silk solution.
15. methods for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 9) described in carbon
Fiber precursor carry out in the state of drawing-off is imposed, in having oxygen atmosphere pre-oxidize three sections of time-division complete, first paragraph oxidizing temperature
For 210～222 DEG C, oxidization time is 20～24min, and drafting multiple is 0～5；Second segment oxidizing temperature is 235～245 DEG C, oxygen
The change time is 20～24min, and drafting multiple is -1～1；3rd section of oxidizing temperature is 255～265 DEG C, oxidization time is 20～
24min, drafting multiple is -1～1.
16. methods for preparing polyacrylonitrile-based carbon fibre according to claim 1 or 15, it is characterised in that step 9) it is described
Have oxygen atmosphere be air.
17. methods for preparing polyacrylonitrile-based carbon fibre according to claim 1, it is characterised in that step 10) described in
Preoxided thread carry out in the state of drawing-off is imposed, in an oxygen-free atmosphere be carbonized two sections of time-division complete, first paragraph carburizing temperature is
350～700 DEG C, carbonization time is 1～2min, and drafting multiple is 3～5 times；Second segment carburizing temperature is 800～1350 DEG C, carbon
The change time is 1～2min, and drafting multiple is -2～0.
18. methods for preparing polyacrylonitrile-based carbon fibre according to claim 1 or 17, it is characterised in that step 10) institute
The oxygen-free atmosphere stated is nitrogen.
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| CN101165238A (en) * | 2006-10-18 | 2008-04-23 | 中国石化上海石油化工股份有限公司 | Method for preparing polyacrylonitrile-based carbon fiber protofilament |
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