CN102953158B - A kind of method of manufacture polyacrylonitrile-based carbon fibre - Google Patents
A kind of method of manufacture polyacrylonitrile-based carbon fibre Download PDFInfo
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Abstract
A kind of method of manufacture polyacrylonitrile-based carbon fibre, the Third monomer of the spinning material polyacrylonitrile resin of its precursor is furoate clothing, and resin NaSCN solutions are into spinning solution, Jing spray webbing and the prepared as-spun fibre of solidification forming.Then as-spun fibre is sequentially passed through：Water-bath drawing-off is carried out in NaSCN aqueous solutions；Deionized water drip washing；It is placed in acidic aqueous solution and impregnates；It is placed in sodium hydroxide or potassium hydroxide aqueous solution and impregnates；Water-bath drawing-off is carried out in pure water；Deionized water is rinsed to rinsing liquid and is further continued for 5～15min of rinsing in neutrality and after not measuring sodium ion or potassium ion.Jing's as-spun fibre oils and compacting by drying last handling process prepared carbon fibre precursor again.Precursor is pre-oxidized in the state of drawing-off is imposed in having oxygen atmosphere, and in the state of drawing-off is imposed, is carbonized in an oxygen-free atmosphere, obtains polyacrylonitrile-based carbon fibre finished product.
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 wet spinning technology.
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, as 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 obtained by function admirable, the purification of precursor are 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 carries out pre-oxidizing, is carbonized at the high-temperature process
CO、CO2Effusion Deng gas is so as to being internally formed cavity blemish in carbon fiber.If measuring metal impurities in precursor to contain with ash
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 therein respectively
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 the purification roguing to precursor is completed 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 the mechanical performance for improving carbon fiber.
Polyacrylonitrile carbon fiber precursor still more adopts inorganic salt or aqueous acid for solvent spinning in a wet process at present
Technique is manufactured, and conventional inorganic salt or acid include NaSCN, ZnCl2And HNO3Deng the wherein industrial applications of NaSCN are the most general
Time.In prior art, the purge process of precursor mainly includes that acid solution is washed and rinses two steps, and fiber first uses acidic aqueous solution
Carry out impregnating washing to clean the metal impurities in fiber, then deionized water rinses fiber to neutrality.It is generally acknowledged that first
Raw fiber carries out washing before not completing drawing-off and has preferable effect, because now fiber still locates gel state, structure is more
Loose, the metal ion of fibrous inside is easily spread to cleaning mixture.This washing methods is for metal impurities in removal fiber
Effect is ideal, but can bring unfavorable to the drawing-off of fiber.This be thoroughly cleaned due to metal impurities after, polyacrylonitrile divides greatly
Subchain underpants health acid unit is carboxylic acid by the form transformation of carboxylate.It is known that the hydrogen atom on carboxylic acid because electronics deviates is in
Existing positive charge, the nitrogen-atoms that it can be big with electronegativity in acrylonitrile unit in strand form hydrogen bond.This hydrogen bond may be present in
Moiety segments cyclization is made in same macromolecular chain, can exist in hands over the moiety segments of adjacent macromole between different macromole
Connection.As the adhesion of hydrogen bond is much larger than general intermolecular model Dehua gravitation, this will cause fiber polymer in drawing-off
Macromole is difficult to be extended and stretches, and the desired result of drawing of fiber is to make all of polymer macromolecule in the presence of external force
It is straightened and obtains the higher degree of orientation.Experiment shows, under the premise of draft ratio and other process conditions identicals, Jing pickling
The drawing-off of as-spun fibre afterwards can become more difficult, and the tensile strength of precursor product is also presented downward trend, while extension at break
It 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, and one
As up to 15% or so, this can undoubtedly have a strong impact on the mechanical performance of carbon fiber finished product.And as-spun fibre enters after completing drawing-off again
Then purification effect is preferable not to the utmost for row washing, because now fibre structure is more closely, is unfavorable for that metal ion expands to cleaning mixture
Dissipate.The ionization constant of particularly alkali earth metal is relatively low, in the alkaline earth gold that Fibrous depth is present with carboxylate form
Category ion is difficult to be removed by pickling, even if reinforcing washing process condition, in precursor product, ash is still difficult under normal circumstances
Reach the level less than 0.1wt ‰.So far, the purification of the above-mentioned precursor of prior art not yet effectively solving and mechanical performance become
Poor this contradiction.
The content of the invention
The invention provides a kind of method of manufacture 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 is prepared using NaSCN aqueous solution wet spinning technologies.This
The purpose that technical problem to be solved is that precursor reaches purification by washing is invented, while protofilament fracture strength does not receive shadow
Ring, 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 of manufacture polyacrylonitrile-based carbon fibre, the spinning material polyacrylonitrile resin of carbon fibre precursor is three kinds
The copolymer of monomer, the first monomer are 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 as solvent with the NaSCN aqueous solutions of 45～58wt%, with 8～
The NaSCN aqueous solutions of 16wt% are that coagulating bath adopts wet spinning technology Jing spray webbing and solidification forming that as-spun fibre is obtained；
2) as-spun fibre carries out water-bath drawing-off in the NaSCN aqueous solutions of 1～5wt%, and bath temperature is controlled to 5～30
DEG C, drafting multiple is controlled to 1.5～2.5；
3) as-spun fibre deionized water drip washing, water temperature are controlled to 45～60 DEG C, and drip washing time control is 2～20min；
4) as-spun fibre is placed in acidic aqueous solution and impregnates, and acid adopts sulphuric acid, hydrochloric acid or nitric acid, the pH value of acidic aqueous solution
For 0.5～3.0, 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 2～15min；
5) as-spun fibre is placed in sodium hydroxide or potassium hydroxide aqueous solution and impregnates, sodium ion in liquor or potassium ion it is dense
Spend for 200～800mg/L, temperature control is 40～60 DEG C, with weight ratio meter, bath raio is controlled to as-spun fibre: solution=1: (5
～10), dip time is controlled to 1～5min；
6) 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
3～5；
7) as-spun fibre temperature is that 90～100 DEG C of deionized water carries out hot bath rinsing, to rinsing liquid in neutral and
5～15min of rinsing is further continued for after not measuring sodium ion or potassium ion；
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 the state of drawing-off is imposed in an oxygen-free atmosphere, obtains polyacrylonitrile-based carbon fine
Dimension finished product.
Above-mentioned steps 4) described in acid preferably with nitric acid；The pH value of acidic aqueous solution preferably 1.0～2.0；Acid water
Preferably 50～55 DEG C of the temperature of solution；Bath raio is preferably controlled to as-spun fibre: solution=1: (18～23)；Dip time is best
It is controlled to 4～8min.
Above-mentioned steps 5) described in sodium ion in liquor or potassium ion concentration be preferably 300～500mg/L；Solution temperature
45～50 DEG C are controlled to preferably；Bath raio is preferably controlled to as-spun fibre: solution=1: (6～8)；Dip time is preferably controlled to 3
～4min.
In bath raio, as-spun fibre weight can press polypropylene in spinning solution again according to the spinning solution extrusion capacity of spinning part
The pure calculating of nitrile resin content.
Above-mentioned steps 7) described in the most handy temperature of as-spun fibre be that 95～98 DEG C of deionized water carries out hot bath rinsing,
Rinsing 7～12min is further continued in neutrality and after not measuring sodium ion or potassium ion to rinsing liquid.
It is same as the prior art, the molecular weight generally 50000～200000 of above-mentioned polyacrylonitrile resin；Above-mentioned steps are 1)
In described spinning solution, polyacrylonitrile resin content general control is 10～14wt%.
9) precursor pre-oxidation can typically divide three sections and complete above-mentioned steps, 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 are -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, washing process
The pickling typically adopted by prior art is changed to a pickling and an alkali liquor neutralization, before washing process is located at drawing-off.
The dipping washing of as-spun fibre elder generation Jing acidic aqueous solutions, the metal impurities being free in fiber between macromole are washed under the action of an acid
Removal is washed, the furoate clothing unit existed with carboxylate form in macromole is then converted into carboxylic acid.Then as-spun fibre Jing alkali liquor leaching
Stain, the furoate clothing unit existed with carboxylic acid form in macromole are then converted to carboxylic acid sodium salt or potassium salt.As-spun fibre is carried out immediately
Drawing-off, is avoided by as the hydrogen atom on the hydroxy-acid group of furoate clothing unit forms hydrogen bond with the nitrogen-atoms of acrylonitrile unit, with
The macromole that machine is curled successfully can be straightened in drawing-off orientation.
As-spun fibre complete drawing-off after again deionized water rinsed, as sodium ion or potassium ion have higher electricity
From constant, as long as rinsing is abundant, deionized water is fully able to reach the sodium ion of bringing aqueous slkali into or potassium ion cleans
Purpose.Inventor is confirmed by experimental data, technique of the as-spun fibre after drawing-off is completed as described in technical solution of the present invention
Condition is rinsed, and the ash of precursor product substantially can be less than 0.1 ‰.
Although the present invention is spin solvent only with NaSCN aqueous solutions, those skilled in the art is not difficult to deduce, other
The conventional inorganic solvent such as HNO of manufacture polyacrylonitrile fibre3、Zncl2Etc. being applied equally to the technical program.
The present invention achieves substantial progress compared with prior art, and protofilament has reached removal by washing is satisfactory
The purpose of metal impurities, purification effect are 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 press GB/T3362-2005 measure, 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, and 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
On electric furnace, in cooling a moment, place in 800 DEG C of high temperature resistance furnace, and calcination 2hr is allowed to be ashed, and after taking out, moves from high temperature furnace
Room temperature is cooled in entering exsiccator, 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 1～12】
1) polyacrylonitrile resin is configured to spinning solution, spinning solution as solvent with the NaSCN aqueous solutions of 45～58wt%
Middle polyacrylonitrile resin content is 10～14wt%.Wet spinning work is adopted by coagulating bath of the NaSCN aqueous solutions of 8～16wt%
Skill Jing spray webbing and solidification forming are obtained as-spun fibre；
2) as-spun fibre carries out water-bath drawing-off in the NaSCN aqueous solutions of 1～5wt%, the bath temperature of each embodiment and
Drafting multiple is shown in Table 1, and this step is defined as front draft in table；
3) as-spun fibre deionized water drip washing, water temperature are controlled to 45～60 DEG C, and drip washing time control is 2～20min；
4) as-spun fibre is placed in acidic aqueous solution and impregnates, acid and pH value, acidity that each embodiment acidic aqueous solution is adopted
The control data of the temperature of aqueous solution, bath raio and dip time etc. is shown in Table 2；
5) as-spun fibre is placed in sodium hydroxide or potassium hydroxide aqueous solution and impregnates, what each embodiment alkaline aqueous solution was adopted
The control data of the concentration of alkali and sodium ion in liquor or potassium ion, the temperature of alkaline aqueous solution, bath raio and dip time etc. is shown in
Table 3；
6) 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
This step is defined as first break draft in table by table 1；
7) as-spun fibre deionized water carries out hot bath rinsing, to rinsing liquid in it is neutral and do not measure sodium ion or potassium from
When continuing rinsing number after son, the temperature of each embodiment hot bath, continue rinsing time and total rinsing time is shown in Table 4；
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.
【Comparative example 1～4】
1)～3) identical with embodiment 1～12, 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；
5) as-spun fibre deionized water carries out hot bath rinsing, to rinsing liquid in neutrality, the temperature of each comparative example hot bath
Degree and rinsing time are shown in Table 4；
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
This step is defined as first break draft in table by table 1；
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 are -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 (17)
1. a kind of method of manufacture 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 are 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 method according to
It is secondary to comprise the following steps：
1) polyacrylonitrile resin is configured to spinning solution as solvent with the NaSCN aqueous solutions of 45～58wt%, with 8～16wt%'s
NaSCN aqueous solutions are that coagulating bath adopts wet spinning technology Jing spray webbing and solidification forming that as-spun fibre is obtained；
2) as-spun fibre carries out water-bath drawing-off in the NaSCN aqueous solutions of 1～5wt%, and bath temperature is controlled to 5～30 DEG C, leads
Stretch multiple and be controlled to 1.5～2.5；
3) as-spun fibre deionized water drip washing, water temperature are controlled to 45～60 DEG C, and drip washing time control is 2～20min；
4) as-spun fibre is placed in acidic aqueous solution and impregnates, and acid using sulphuric acid, hydrochloric acid or nitric acid, the pH value of acidic aqueous solution is
0.5～3.0, 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 2～15min；
5) as-spun fibre is placed in sodium hydroxide or potassium hydroxide aqueous solution and impregnates, and the concentration of sodium ion in liquor or potassium ion is
200～800mg/L, temperature control are 40～60 DEG C, and with weight ratio meter, bath raio is controlled to as-spun fibre: solution=1: (5～
10), dip time is controlled to 1～5min；
6) 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 3～
5；
7) as-spun fibre temperature is that 90～100 DEG C of deionized water carries out hot bath rinsing, to rinsing liquid in neutral and survey not
5～15min of rinsing is further continued for after going out sodium ion or potassium ion；
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 the state of drawing-off is imposed in an oxygen-free atmosphere, obtain polyacrylonitrile-based carbon fibre into
Product.
2. it is according to claim 1 manufacture polyacrylonitrile-based carbon fibre method, it is characterised in that step 4) described in acid
Using nitric acid.
3. it is according to claim 1 manufacture polyacrylonitrile-based carbon fibre method, it is characterised in that step 4) described in acid
Property aqueous solution pH value be 1.0～2.0.
4. it is according to claim 1 manufacture polyacrylonitrile-based carbon fibre method, it is characterised in that step 4) described in acid
Property aqueous solution temperature be 50～55 DEG C.
5. it is according to claim 1 manufacture polyacrylonitrile-based carbon fibre method, it is characterised in that step 4) described in bath
Than being controlled to as-spun fibre: solution=1: (18～23).
6. it is according to claim 1 manufacture polyacrylonitrile-based carbon fibre method, it is characterised in that step 4) described in leaching
Stain time control is 4～8min.
7. it is according to claim 1 manufacture polyacrylonitrile-based carbon fibre method, it is characterised in that step 5) described in it is molten
In liquid, the concentration of sodium ion or potassium ion is 300～500mg/L.
8. it is according to claim 1 manufacture polyacrylonitrile-based carbon fibre method, it is characterised in that step 5) described in it is molten
Liquid temp is controlled to 45～50 DEG C.
9. it is according to claim 1 manufacture polyacrylonitrile-based carbon fibre method, it is characterised in that step 5) described in bath
Than being controlled to as-spun fibre: solution=1: (6～8).
10. it is according to claim 1 manufacture polyacrylonitrile-based carbon fibre method, it is characterised in that step 5) described in leaching
Stain time control is 3～4min.
The methods of 11. manufacture polyacrylonitrile-based carbon fibres according to claim 1, it is characterised in that step 7) described in just
Raw fiber temperature is that 95～98 DEG C of deionized water carries out hot bath rinsing, to rinsing liquid in it is neutral and do not measure sodium ion or
7～12min of rinsing is further continued for after potassium ion.
The method of 12. manufacture polyacrylonitrile-based carbon fibres according to claim 1, it is characterised in that described polyacrylonitrile
The molecular weight of resin is 50000～200000.
13. it is according to claim 1 manufacture polyacrylonitrile-based carbon fibres methods, it is characterised in that step 1) described in spinning
In silk solution, polyacrylonitrile resin content is 10～14wt%.
14. it is according to claim 1 manufacture polyacrylonitrile-based carbon fibres methods, 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 are -1～1.
The method of the 15. manufacture polyacrylonitrile-based carbon fibres according to claim 1 or 11, it is characterised in that step 9) it is described
Have oxygen atmosphere be air.
The method of 16. manufacture polyacrylonitrile-based carbon fibres 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.
The method of the 17. manufacture polyacrylonitrile-based carbon fibres according to claim 1 or 13, it is characterised in that step 10) institute
The oxygen-free atmosphere stated is nitrogen.
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| CN105862177B (en) * | 2016-04-19 | 2018-11-16 | 郑州四维特种材料有限责任公司 | A kind of method and system for recycling tail gas and carbon fiber being surface-treated |
| CN109763318B (en) * | 2018-12-13 | 2021-04-16 | 南京工程学院 | Alkaline carbon nanofiber with three-dimensional pore structure |
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