CN102953145B - The method preparing polyacrylonitrile base carbon fiber precursors - Google Patents
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Abstract
A kind of method preparing polyacrylonitrile base carbon fiber precursors, the Third monomer of 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;Then as-spun fibre sequentially passes through: carry out water-bath drawing-off in the aqueous solution of spin solvent;Use deionized water drip washing;Being placed in the buffer solution containing acid A and salt B and impregnate, A is nitric acid, sulphuric acid or hydrochloric acid, and B is sodium salt or the potassium salt of A;Water-bath drawing-off is carried out in pure water;It is placed in acidic aqueous solution dipping;With deionized water rinsing to rinsing liquid be neutrality;As-spun fibre is again through oiling and the last handling process such as compacting by drying makes polyacrylonitrile base carbon fiber precursors product.Present invention solves the technical problem that it is that precursor reaches the purpose of purification by washing, fibrous fracture intensity is unaffected simultaneously, thus compensate for the defect that prior art exists.
Description
Technical field
The method that the present invention relates to manufacture polyacrylonitrile base carbon fiber precursors, particularly to being the 3rd altogether to use furoate clothing
The polyacrylonitrile resin of poly-monomer, as spinning material, manufactures the side of polyacrylonitrile base carbon fiber precursors by solution spinning processes
Method.
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 a kind of method preparing polyacrylonitrile base carbon fiber precursors, spinning material for using furoate clothing is
The polyacrylonitrile resin of trimerization monomer, and use the solution spinning processes with DMSO or DMAC as spin solvent.Institute of the present invention
Solving the technical problem that it is that precursor reaches the purpose of purification by washing, fibrous fracture intensity is unaffected simultaneously, thus more
Mend the defect that prior art exists.
The following is the present invention and solve the technical scheme that above-mentioned technical problem is concrete:
A kind of method preparing polyacrylonitrile base carbon fiber precursors, spinning material polyacrylonitrile resin is being total to of three kinds of monomers
Polymers, the first monomer is acrylonitrile;Second comonomer takes from acrylic acid methyl ester., ethyl acrylate, methyl methacrylate, methyl-prop
One in olefin(e) acid ethyl ester or vinylacetate;Third monomer is furoate clothing.In polyacrylonitrile resin, the content of Third monomer is
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) 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, buffers molten
It is 45~60 DEG C that the temperature of liquid controls, and with mass ratio range, bath raio controls as as-spun fibre: buffer solution=1: (15~25), leaching
The control of stain time is 2~10min;
5) 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;
6) 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 3.0~5.0, 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 2~8min that dip time controls;
7) as-spun fibre temperature is that the deionized water of 90~100 DEG C carries out hot bath rinsing, until rinsing liquid is neutrality;
8) the post-treated process of as-spun fibre prepares polyacrylonitrile base carbon fiber precursors product, and last handling process includes oiling
And compacting by drying.
Above-mentioned steps 4) described in A be preferably nitric acid, B is preferably sodium nitrate;The pH value of buffer solution be 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 control as as-spun fibre: buffer solution=1: (18~23);Dip time preferably controls to be 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 preferably controls as as-spun fibre: solution=1: (18~23);Dip time preferably control be 3~
5min。
In above-mentioned bath raio, as-spun fibre weight can be pressed in spinning solution poly-according to the spinning solution extrusion capacity of spinning part again
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 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%.
The essence of the present invention is when as-spun fibre carries out washing removal metal impurities, and cleaning mixture is general by prior art
The acid solution used changes into a kind of containing mineral acid and corresponding sodium salt thereof or the buffer solution of potassium salt.Washing step is positioned at and leads
Before stretching, after the washing of as-spun fibre buffered solution impregnation, the metal impurities being free in fiber between macromole are in the effect of acid
Under be washed to remove, in macromole with carboxylate form exist furoate clothing unit on alkaline earth metal atom be then buffered solution
In sodium ion or potassium ion replace, become sodium salt or potassium salt, and be not converted into carboxylic acid.The buffered solution impregnation of as-spun fibre is washed
Drawing-off is carried out immediately, owing to the nitrogen-atoms of the hydrogen atom on the hydroxy-acid group of furoate clothing unit with acrylonitrile unit forms hydrogen after washing
Key is avoided by, and the macromole curled at random can successfully be straightened when drawing-off orientation.
Sodium ion or potassium ion are cleaned after completing drawing-off by as-spun fibre again with acid solution, enter with deionized water the most again
Row rinsing.Owing to sodium ion or potassium ion have higher ionization constant, complete the as-spun fibre of drawing-off through pickling again and
The purpose that the sodium ion being entirely capable of reaching to be brought into by buffer solution after deionized water rinsing or potassium ion are cleaned.Inventor is by testing
Data are confirmed, and as-spun fibre process conditions as described in technical solution of the present invention after completing drawing-off carry out pickling and drift
Washing, the ash of precursor product the most all can be less than 0.1 ‰.
Commonly used, as long as sodium salt or potassium salt have good in theory when the acid selected in buffer solution is by prior art pickling
Water solublity and easily ionization decomposer, but for making rinsing process more easy to control, acid and salt preferably take both and have identical acid
Root.
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 fiber has reached removal metal by washing is satisfactory
The purpose of impurity, purification effect is the best.The drawing-off of fiber then can be smooth, the broken filament of precursor product
Intensity can improve 10~about 20% relatively, and single fiber extension at break can reduce by 5~about 10%, and invention effect is the most obvious.
Below by specific embodiment, the invention will be further described.Owing to washing process is the master of the present invention
Wanting distinguishing characteristics, spinning material, other spinning and aftertreatment technology etc. are all essentially identical with prior art, therefore embodiment and ratio
Relatively example will focus on enumerating of washing process and draft process condition, and correspondingly shows reflection washing and the property of drawing-off effect
Energy index test data, such as ash, broken filament intensity and the extension at break of precursor.Other conventional index of precursor and the present invention
Distinguishing characteristics there is not obvious relatedness, embodiment and comparative example will it will not go into details.
In embodiment and comparative example, broken filament intensity and extension at break are pressed GB/T 14335-2008 and are measured, ash
Assay method see 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
Entering and be cooled to room temperature in exsiccator, weighing, (quality is m1)。
It is calculated as follows ash:
Detailed description of the invention
The spinning material polyacrylonitrile resin that embodiment and comparative example use is prepared by aqueous suspension polymerization technique, except third
Second, third comonomer outside alkene nitrile is respectively acrylic acid methyl ester. and itaconic acid, and the weight ratio of three is 97: 2: 1, acrylonitrile
The molecular weight of resin is 90000.The ash recording polyacrylonitrile resin raw material is 1.62 ‰.
[embodiment 1~10]
Carry out the preparation of carbon fibre precursor according to the following steps:
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) as-spun fibre is placed in the buffer solution containing acid A and salt B and impregnates, each embodiment buffer solution composition and pH
The control data of value, the temperature of buffer solution, bath raio and dip time etc. are shown in Table 2 and 3;
5) 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;
6) during as-spun fibre is placed in acidic aqueous solution impregnate, each embodiment acidic aqueous solution use acid, pH value and temperature,
The control data of bath raio, dip time etc. are shown in Table 4;
7) as-spun fibre temperature is that the deionized water of 90~100 DEG C carries out hot bath rinsing, until rinsing liquid is neutrality;
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 product.
[embodiment 11~12]
Carry out the preparation of carbon fibre precursor according to the following steps:
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]
Carry out the preparation of carbon fibre precursor according to the following steps:
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 and 3;
5) as-spun fibre temperature is that the deionized water of 90~100 DEG C carries out hot bath rinsing, is neutrality to rinsing liquid;
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 product.
Test each embodiment and the ash of comparative example precursor product, broken filament intensity and extension at break, the results are shown in Table
5。
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Claims (14)
1. the method preparing polyacrylonitrile base carbon fiber precursors, spinning material polyacrylonitrile resin is the copolymerization of three kinds of monomers
Thing, the first monomer is acrylonitrile;Second comonomer takes from acrylic acid methyl ester., ethyl acrylate, methyl methacrylate, metering system
One in acetoacetic ester or vinylacetate;Third monomer is furoate clothing, and in polyacrylonitrile resin, the content of Third monomer is 0.5
~2.0wt%, and second and the total content of Third monomer be 1.0~7.0wt%, it is characterised in that this preparation method includes successively
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) 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
It is 45~60 DEG C that temperature controls, and with mass ratio range, bath raio controls as as-spun fibre: buffer solution=1: (15~25), during dipping
Between control be 2~10min;
5) 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;
6) 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
3.0~5.0, 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 2~8min;
7) as-spun fibre temperature is that the deionized water of 90~100 DEG C carries out hot bath rinsing, until rinsing liquid is neutrality;
8) the post-treated process of as-spun fibre makes polyacrylonitrile base carbon fiber precursors product, and last handling process includes oiling and doing
Dry densification.
The method preparing polyacrylonitrile base carbon fiber precursors the most according to claim 1, it is characterised in that step 4) described
A be nitric acid, B is sodium nitrate.
The method preparing polyacrylonitrile base carbon fiber precursors the most according to claim 1, it is characterised in that step 4) described
The pH value of buffer solution be 2.5~3.5.
The method preparing polyacrylonitrile base carbon fiber precursors the most according to claim 1, it is characterised in that step 4) described
Sodium ion or the concentration of potassium ion be 300~500mg/L.
The method preparing polyacrylonitrile base carbon fiber precursors the most according to claim 1, it is characterised in that step 4) described
The temperature of buffer solution be 45~55 DEG C.
The method preparing polyacrylonitrile base carbon fiber precursors the most according to claim 1, it is characterised in that step 4) described
Bath raio control as as-spun fibre: buffer solution=1: (18~23).
The method preparing polyacrylonitrile base carbon fiber precursors the most according to claim 1, it is characterised in that step 4) described
Dip time control be 4~8min.
The method preparing polyacrylonitrile base carbon fiber precursors the most according to claim 1, it is characterised in that step 6) described
The pH value of acidic aqueous solution be 3.5~4.5.
The method preparing polyacrylonitrile base carbon fiber precursors the most according to claim 1, it is characterised in that step 6) described
Acidic aqueous solution temperature control be 50~55 DEG C.
The method preparing polyacrylonitrile base carbon fiber precursors the most according to claim 1, it is characterised in that step 6) described
Bath raio control as as-spun fibre: solution=1: (18~23).
11. methods preparing polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterised in that step 6) described
Dip time control be 3~5min.
12. methods preparing polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterised in that described poly-third
The molecular weight of alkene nitrile resin is 50000~200000.
13. methods preparing polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterised in that step 1) described
Polyacrylonitrile resin be configured to spinning solution with DMSO for spin solvent, with the aqueous solution of DMSO that concentration is 30~50wt%
Solution spinning processes is used to prepare as-spun fibre through spray webbing and solidification forming for coagulating bath.
14. methods preparing polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterised in that step 1) described
Spinning solution in polyacrylonitrile resin content be 18~25wt%.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4507272A (en) * | 1983-05-09 | 1985-03-26 | Hitco | Method of purifying partially carbonized pan material prior to carbonization |
JP2004238761A (en) * | 2003-02-06 | 2004-08-26 | Toray Ind Inc | Carbon fiber strand and fiber-reinforced composite material |
CN101161694A (en) * | 2007-11-22 | 2008-04-16 | 吉林奇峰化纤股份有限公司 | Preparation method of polymer for polyacrylonitrile base carbon fiber precursors |
CN101165072A (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 removing alkali metal impurity in polyacrylonitrile resin |
CN101165237A (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 |
CN100570026C (en) * | 2006-10-18 | 2009-12-16 | 中国石化上海石油化工股份有限公司 | The manufacture method of polyacrylonitrile base carbon fiber precursors |
-
2011
- 2011-08-25 CN CN201110244719.6A patent/CN102953145B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4507272A (en) * | 1983-05-09 | 1985-03-26 | Hitco | Method of purifying partially carbonized pan material prior to carbonization |
JP2004238761A (en) * | 2003-02-06 | 2004-08-26 | Toray Ind Inc | Carbon fiber strand and fiber-reinforced composite material |
CN101165072A (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 removing alkali metal impurity in polyacrylonitrile resin |
CN101165237A (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 |
CN100570026C (en) * | 2006-10-18 | 2009-12-16 | 中国石化上海石油化工股份有限公司 | The manufacture method of polyacrylonitrile base carbon fiber precursors |
CN101161694A (en) * | 2007-11-22 | 2008-04-16 | 吉林奇峰化纤股份有限公司 | Preparation method of polymer for polyacrylonitrile base carbon fiber precursors |
Non-Patent Citations (1)
Title |
---|
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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