CN102953154B - A kind of manufacture method of polyacrylonitrile-based carbon fibre - Google Patents
A kind of manufacture method of polyacrylonitrile-based carbon fibre Download PDFInfo
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Abstract
The manufacture method of a kind of polyacrylonitrile-based carbon fibre, the Third monomer of its precursor spinning material polyacrylonitrile resin is furoate clothing, and resin DMSO or DMAC is configured to spinning solution, prepares as-spun fibre through spray webbing and solidification forming.As-spun fibre passes through subsequently: carry out water-bath drawing-off in the aqueous solution of spin solvent；Use deionized water drip washing；It is placed in acidic aqueous solution dipping 2～10min；It is placed in sodium hydroxide or potassium hydroxide aqueous solution dipping 1～5min；Water-bath drawing-off is carried out in pure water；Carry out hot bath rinsing with deionized water, be further continued for rinsing 5～15min in neutrality and after not measuring sodium ion or potassium ion to rinsing liquid.As-spun fibre is again through oiling and the last handling process such as compacting by drying prepares carbon fibre precursor, precursor pre-oxidizes in having oxygen atmosphere when imposing drawing-off, carry out carbonization again when imposing drawing-off in an oxygen-free atmosphere, obtain polyacrylonitrile-based carbon fibre finished product.
Description
Technical field
The present invention relates to manufacture polyacrylonitrile-based carbon fibre method, the precursor of carbon fiber prepare raw material polyacrylonitrile tree
Fat uses furoate clothing to be the 3rd comonomer, and precursor is prepared by solution spinning processes.
Background technology
Carbon fiber has the mechanical property of excellence, and its high specific strength and other material of specific modulus 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
The precursor that carbonization material is made prepares after pre-oxidation and carbonization, owing to polyacrylonitrile resin has higher carbonization yield, because of
This polyacrylonitrile fibre is ideal carbon fibre precursor, and prepared carbon fiber is referred to as polyacrylonitrile-based carbon fibre.
The polyacrylonitrile-based carbon fibre of function admirable to be obtained, the purification of precursor is most important, especially contains metal impurities
The requirement of amount is higher, during the high-temperature process such as such as alkali and alkaline earth metal ions, they carry out pre-oxidizing at precursor, carbonization, can promote
CO、CO2Deng the effusion of gas thus it is internally formed cavity blemish at carbon fiber.If measuring metal impurities in precursor with ash to contain
Amount, when ash is less than 0.1 ‰, precursor is generally considered to be High Purity, and thus obtained carbon fiber will have higher product
Matter.
Metal class impurity in polyacrylonitrile base carbon fiber precursors is essentially from polymer raw, polymerization initiation system and gathers
Close or the solvent of spinning.Removal for metal impurities can be after the last handling process of precursor manufacture, precursor be made or precursor warp
Link uses the means of washing to carry out after pre-oxidation etc., and prior art is the most first washed with acidic aqueous solution, then spends
Ionized water rinses.United States Patent (USP) US 3,413,094, US 4,113,847, US 4,507,272 describe therein respectively
Portion of techniques, " pickling of PAN base fibre carbon fiber precursor and the discussion of ion diffusion mechanism " [" Donghua University's journal (natural section
Learn version) " 06 phase in 1993] PAN as-spun fibre, finished fiber and pre-oxidized fibers then wash by a literary composition, 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.The most industrial
Before pre-oxidation, generally just complete the purification roguing to precursor process, because metal impurities can be to pre-oxidation when pre-oxidation
The structure of silk damages.
As manufacture with common acrylon, the spinning material polyacrylonitrile resin of polyacrylonitrile base carbon fiber precursors not third
The homopolymer of a kind of monomer of alkene nitrile polymerization, it must containing the second comonomer of 2～about 5wt%, conventional as acrylic acid methyl ester.,
Ethyl acrylate, methyl methacrylate, ethyl methacrylate or vinylacetate etc..The existence 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
Possibly together with the Third monomer of 0.5～2.0wt%, the most frequently used for itaconic acid, the existence in itaconic acid can change polyacrylonitrile in advance
Thermal cyclization reaction behavior during oxidation, reduces oxidation reaction initial temperature and peak temperature, makes oxidation reaction heat release mild, Wen Feng
Wider, oxidizing process carries out the most thorough, this mechanical performance being conducive to improving carbon fiber.
Except NaSCN, ZnCl2And HNO3Deng inorganic salt or aqueous acid as spin solvent beyond, current polyacrylonitrile carbon
Fiber precursor the most more uses dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and dimethyl acetylamide (DMAC) etc.
Organic solvent is that spin solvent manufactures with solution spinning processes, and wherein the industrial applications of DMSO and DMAC is the most universal.Existing
Having the purge process of precursor in technology mainly to include acid solution washing and two steps of rinsing, fiber first soaks with acidic aqueous solution
Stain is washed with the metal impurities in clean fiber, then with deionized water by the most neutral for fiber rinsing.It is generally acknowledged at as-spun fibre
Carrying out washing before being not fully complete drawing-off and have preferable effect, because now gel state still located by fiber, structure is the most loose, fine
Metal ion within Wei easily spreads to cleaning mixture.This washing methods is for the effect of metal impurities in removal fiber very
Ideal, but the drawing-off of fiber can be brought unfavorable.This be thoroughly clean due to metal impurities 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 presents positive charge because electronics deviates,
The nitrogen-atoms that its meeting is big with electronegativity in acrylonitrile unit in strand forms hydrogen bond.This hydrogen bond may be present in same macromole
Chain makes moiety segments cyclization, the moiety segments crosslinking of the adjacent macromole of chien shih of different macromole can be existed in.Due to hydrogen
The adhesion of key is much larger than general intermolecular model Dehua gravitation, and this will cause fiber polymer macromolecule when drawing-off to be difficult to
It is extended and stretches, and the desired result of drawing of fiber is to make all of polymer macromolecule be straightened under the effect of external force and obtain
The degree of orientation that must be higher.Experiment shows, on the premise of draft ratio and other process conditions are identical, and as-spun fibre after pickling
Drawing-off can become more difficulty, the hot strength of precursor product also presents downward trend, and extension at break is in rising trend simultaneously.
Generally single fiber extension at break rises about about 5%, and the lower reduction of broken filament intensity then becomes apparent from, typically left up to 15%
The right side, this can have a strong impact on the mechanical performance of carbon fiber finished product undoubtedly.As-spun fibre carries out washing then purification after completing drawing-off again
Effect is the most preferable, because now fibre structure is the tightst, is unfavorable for that metal ion spreads to cleaning mixture.Particularly alkaline earth
The ionization constant of metallic element is relatively low, is in the alkaline-earth metal ions that Fibrous depth exists with carboxylate form and is difficult to pass through
Pickling is removed, even if strengthening washing process condition, in precursor product, ash is still difficult to reach less than 0.1wt ‰ under normal circumstances
Level.Up to now, prior art the most effectively solves purification and this contradiction of mechanical degradation of above-mentioned precursor.
Summary of the invention
The invention provides the manufacture method of a kind of polyacrylonitrile-based carbon fibre, the spinning material of carbon fibre precursor is for using
Furoate clothing is the polyacrylonitrile resin of the 3rd comonomer, and precursor uses DMSO or DMAC to be the solution spinning processes of spin solvent
Prepared.The technical problem to be solved is that precursor reaches the purpose of purification by washing, and protofilament breaks simultaneously
Resistance to spalling is unaffected, it is thus possible to obtain the carbon fiber product of good mechanical performance, to make up the defect that prior art exists.
The following is the present invention and solve the technical scheme that above-mentioned technical problem is concrete:
The manufacture method of a kind of 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 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 the total content of Third monomer be 1.0～7.0wt%.
The method comprises the following steps successively:
1) polyacrylonitrile resin is configured to spinning solution with DMSO or DMAC for spin solvent, is 30～50wt% with concentration
The aqueous solution of spin solvent be that coagulating bath uses solution spinning processes to prepare as-spun fibre through 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%
Control is 85～100 DEG C, and it is 3.5～5.0 that drafting multiple controls；
3) as-spun fibre deionized water drip washing, it is 45～60 DEG C that water temperature controls, and the control of drip washing time is 2～20min；
4) impregnating during as-spun fibre is placed in acidic aqueous solution, acid uses nitric acid, sulphuric acid or hydrochloric acid, the pH value of acidic aqueous solution
Being 2.0～4.0, it is 45～60 DEG C that temperature controls, and with mass ratio range, bath raio controls as as-spun fibre: solution=1: (15～25),
It is 2～10min that dip time controls；
5) during as-spun fibre is placed in sodium hydroxide or potassium hydroxide aqueous solution, dipping, sodium ion in liquor or potassium ion is dense
Degree is 200～800mg/L, and it is 40～60 DEG C that temperature controls, and with mass ratio range, bath raio controls as as-spun fibre: solution=1: (5
～10), it is 1～5min that dip time controls；
6) as-spun fibre carries out water-bath drawing-off in pure water, and it is 95～100 DEG C that bath temperature controls, and drafting multiple control is
1.3～2.0；
7) as-spun fibre temperature is that the deionized water of 90～100 DEG C carries out hot bath rinsing, to rinsing liquid in neutral and
It is further continued for after not measuring sodium ion or potassium ion rinsing 5～15min；
8) the post-treated process of as-spun fibre prepares carbon fibre precursor, and last handling process includes oiling and compacting by drying；
9) carbon fibre precursor is when imposing drawing-off, pre-oxidizes in having oxygen atmosphere, obtains preoxided thread；
10) preoxided thread is when imposing drawing-off, carries out carbonization 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 is preferably 2.5～3.5；；Acid water
The temperature of solution is preferably 50～55 DEG C；Bath raio preferably controls as as-spun fibre: solution=1: (18～23)；Dip time is best
Control is 4～8min.
Above-mentioned steps 5) described in sodium ion in liquor or the concentration of potassium ion be preferably 300～500mg/L；Solution temperature
Preferably controlling is 45～50 DEG C；Bath raio preferably controls as as-spun fibre: solution=1: (6～8)；Dip time preferably controls to be 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 deionized water that the most handy temperature of as-spun fibre is 95～98 DEG C carry out hot bath rinsing,
It is further continued for rinsing 7～12min to rinsing liquid in neutrality and after not measuring sodium ion or potassium ion.
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 with DMSO for spin solvent, is preferably 30～50wt% with concentration
The aqueous solution of DMSO is that coagulating bath uses solution spinning processes to prepare as-spun fibre through spray webbing and solidification forming；Spinning solution gathers
Acrylonitrile resin content general control is 18～25wt%.
Above-mentioned steps 9) described precursor pre-oxidation typically can 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 is 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 the further carbonization of preoxided thread typically can divide two sections and complete, first paragraph carburizing temperature
Being 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 used by prior art changes a pickling into and an alkali liquor neutralizes, before washing process is positioned at drawing-off.
As-spun fibre first through acidic aqueous solution dipping washing, is free on the metal impurities between macromole and is washed under the action of an acid in fiber
Washing removal, the furoate clothing unit existed with carboxylate form in macromole is then converted into carboxylic acid.Then as-spun fibre soaks through alkali liquor
Stain, the furoate clothing unit existed with carboxylic acid form in macromole is then converted to carboxylic acid sodium salt or potassium salt.As-spun fibre is carried out immediately
Drawing-off, is avoided by owing to the nitrogen-atoms of the hydrogen atom on the hydroxy-acid group of furoate clothing unit with acrylonitrile unit forms hydrogen bond, with
The macromole that machine is curled can successfully be straightened when drawing-off orientation.
As-spun fibre rinses with deionized water after completing drawing-off again, owing to sodium ion or potassium ion have higher electricity
From constant, as long as rinsing is fully, the sodium ion being fully able to reach to be brought into by aqueous slkali with deionized water or potassium ion are cleaned
Purpose.Inventor is confirmed by experimental data, as-spun fibre technique as described in technical solution of the present invention after completing drawing-off
Condition rinses, and the ash of precursor product the most all can be less than 0.1 ‰.
Although the present invention is spin solvent only with DMSO or DMAC, but those skilled in the art is not difficult to deduce, other
The organic solvent such as DMF manufacturing polyacrylonitrile fibre conventional is applied equally to the technical program.
Compared with prior art the present invention achieves substantial progress, and protofilament is removed by satisfactory having reached of washing
The purpose of metal impurities, purification effect is the best.The drawing-off of fiber then can be smooth, the broken filament of precursor
Intensity can improve 10～about 20% relatively, and single fiber extension at break can reduce by 5～about 10%, thus the machinery of carbon fiber product
Performance significantly improves.
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 the most pre-
The processes such as oxidation and carbonization are all essentially identical with prior art, and therefore embodiment and comparative example will focus on time prepared by precursor
Enumerating of washing process and draft process condition, and correspondingly show reflection precursor washing and the testing performance index of drawing-off effect
Data, such as ash, broken filament intensity and the extension at break of precursor, and carbon fiber product associated therewith is relevant refers to
Mark, such as the hot strength of carbon fiber.
In embodiment and comparative example, precursor broken filament intensity and extension at break are pressed GB/T 14335-2008 and are measured,
The hot strength of carbon fiber, stretch modulus are pressed GB/T3362-2005 and are measured, and the assay method of precursor ash sees below
Take the sample (quality is m, is accurate to 0.0001g) of about 4g, be placed in through 800 DEG C of temperature calcinations to constant weight (quality
For m0) porcelain crucible in, will be equipped with the crucible of sample and be placed on electric furnace heating 10～30min, burn to sample and be ashed without black smoke.In
On electric furnace, in cooling a moment, place in the high temperature resistance furnace of 800 DEG C, and calcination 2hr is allowed to be ashed, and after taking out, moves from high temperature furnace
Enter and exsiccator is cooled to room temperature, weigh (quality is ml).
It is calculated as follows ash:
Detailed description of the invention
The spinning material polyacrylonitrile resin that embodiment and the preparation of comparative example precursor use is by aqueous suspension polymerization technique
Prepare,
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 recording polyacrylonitrile resin raw material is 1.62 ‰.
One, the preparation of carbon fibre precursor:
[embodiment 1～10]
1) using DMSO is that polyacrylonitrile resin is configured to spinning solution by solvent, and in spinning solution, polyacrylonitrile resin contains
Amount is 18～25wt%.DMSO aqueous solution with 30～50wt% uses solution spinning processes through spray webbing and to be frozen into for coagulating bath
Shape prepares as-spun fibre；
2) as-spun fibre carries out water-bath drawing-off in the DMSO aqueous solution of 20～30wt%, the bath temperature of each embodiment and
Drafting multiple is shown in Table 1, in table, this step is defined as front draft；
3) as-spun fibre deionized water drip washing, it is 45～60 DEG C that water temperature controls, and the control of drip washing time is 2～20min；
4) impregnate during as-spun fibre is placed in acidic aqueous solution, the acid of each embodiment acidic aqueous solution employing and pH value, acidity
The control data of the temperature of aqueous solution, bath raio and dip time etc. are shown in Table 2；
5) impregnating during as-spun fibre is placed in sodium hydroxide or potassium hydroxide aqueous solution, each embodiment alkaline aqueous solution uses
The control data of alkali and sodium ion in liquor or the concentration of potassium ion, the temperature of alkaline aqueous solution, bath raio and dip time etc. are shown in
Table 3；
6) as-spun fibre carries out water-bath drawing-off in pure water, and the control data of each embodiment bath temperature and drafting multiple are shown in
Table 1, is defined as first break draft by this step in table；
7) as-spun fibre deionized water carries out hot bath rinsing, to rinsing liquid in neutral and do not measure sodium ion or potassium from
When continuing rinsing number after son, the temperature of each embodiment hot bath, continuation rinsing time and total rinsing time are shown in Table 4；
8) as-spun fibre is through oiling 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) using DMAC is that polyacrylonitrile resin is configured to spinning solution by solvent, and in spinning solution, polyacrylonitrile resin contains
Amount is 18～25wt%.DMAC aqueous solution with 30～50wt% uses solution spinning processes through spray webbing and to be frozen into for coagulating bath
Shape prepares 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) during as-spun fibre is placed in acidic aqueous solution impregnate, each comparative example acidic aqueous solution use acid, pH value, temperature,
The control data of bath raio and dip time etc. are shown in Table 2；
5) as-spun fibre deionized water carries out hot bath rinsing, is neutrality to rinsing liquid, the temperature of each comparative example hot bath
Degree and rinsing time are shown in Table 4；
6) as-spun fibre carries out water-bath drawing-off in pure water, and the control data of each comparative example bath temperature and drafting multiple are shown in
Table 1, is defined as first break draft by this step in table；
7) as-spun fibre is through oiling and the last handling process such as compacting by drying, obtains the polyacrylonitrile that fiber number is 1.22dtex
Base carbon fiber protofilament.
Testing each embodiment and the ash of precursor, broken filament intensity and extension at break that comparative example obtains, result is shown in
Table 5.
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Two, carbon fiber is prepared by precursor:
[embodiment 13～20, comparative example 5～6]
Choose above-described embodiment 1～12 and the part precursor that obtains of comparative example 1～4 prepare carbon fiber further, choose
Precursor is shown in Table listed by 6.
Precursor is first through pre-oxidizing to obtain preoxided thread.Pre-oxidation is carried out in atmosphere, divides three sections and completes, first paragraph oxidizing temperature
Being 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 be 20～
24min, drafting multiple is-1～1；
Preoxided thread carries out carbonization further in nitrogen, and carbonization divides two sections to complete, first paragraph carburizing temperature be 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
Being 1～2min, drafting multiple is-2～0.
Then preparing polyacrylonitrile-based carbon fibre product, its specification is: 12k, monofilament average diameter 7 μm.
The hot strength of the carbon fiber that testing example 13～20, comparative example 5～6 obtain and stretch modulus, the results are shown in Table
6。
Table 6.
Claims (3)
1. a manufacture method for 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 in ethyl methacrylate or vinylacetate；Third monomer is furoate clothing, Third monomer in polyacrylonitrile resin
Content is 0.5～2.0wt%, and second and the total content of Third monomer be 1.0～7.0wt%, it is characterised in that the method depends on
Secondary comprise the following steps:
1) polyacrylonitrile resin is configured to spinning solution with DMSO or DMAC for spin solvent, is 30～50wt% spin with concentration
The aqueous solution of silk solvent is that coagulating bath uses solution spinning processes to prepare as-spun fibre through spray webbing and solidification forming；
2) as-spun fibre carries out water-bath drawing-off in the aqueous solution of the spin solvent that concentration is 20～30wt%, and bath temperature controls
Being 85～100 DEG C, it is 3.5～5.0 that drafting multiple controls；
3) as-spun fibre deionized water drip washing, it is 45～60 DEG C that water temperature controls, and the control of drip washing time is 2～20min；
4) impregnating during as-spun fibre is placed in acidic aqueous solution, acid uses nitric acid, sulphuric acid or hydrochloric acid, and the pH value of acidic aqueous solution is
2.0～4.0, it is 45～60 DEG C that temperature controls, and with mass ratio range, bath raio controls as as-spun fibre: solution=1: (15～25), leaching
The control of stain time is 2～10min；
5) impregnating during as-spun fibre is placed in sodium hydroxide or potassium hydroxide aqueous solution, the concentration of sodium ion in liquor or potassium ion is
200～800mg/L, it is 40～60 DEG C that temperature controls, and with mass ratio range, bath raio controls as as-spun fibre: solution=1: (5～
10), dip time controls is 1～5min；
6) as-spun fibre carries out water-bath drawing-off in pure water, and it is 95～100 DEG C that bath temperature controls, and it is 1.3 that drafting multiple controls
～2.0；
7) as-spun fibre temperature is that the deionized water of 90～100 DEG C carries out hot bath rinsing, to rinsing liquid in neutral and survey not
It is further continued for after going out sodium ion or potassium ion rinsing 5～15min；
8) the post-treated process of as-spun fibre prepares carbon fibre precursor, and last handling process includes oiling and compacting by drying；
9) carbon fibre precursor is when imposing drawing-off, pre-oxidizes in having oxygen atmosphere, obtains preoxided thread；
10) preoxided thread is when imposing drawing-off, carries out carbonization in an oxygen-free atmosphere, obtains polyacrylonitrile-based carbon fibre
Product.
The manufacture method of polyacrylonitrile-based carbon fibre the most according to claim 1, it is characterised in that step 4) described in acid
Use nitric acid.
The manufacture method of polyacrylonitrile-based carbon fibre the most according to claim 1, it is characterised in that step 4) described in acid
The pH value of property aqueous solution is 2.5～3.5.
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| 碳纤维用聚丙烯腈原丝制备技术的研究进展;于淑娟等;《高科技纤维与应用》;20031230;第28卷(第06期);15-18 * |
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