CN102953138A - Manufacturing method for polyacrylonitrile-based carbon fiber protofilament - Google Patents
Manufacturing method for polyacrylonitrile-based carbon fiber protofilament Download PDFInfo
- Publication number
- CN102953138A CN102953138A CN2011102446314A CN201110244631A CN102953138A CN 102953138 A CN102953138 A CN 102953138A CN 2011102446314 A CN2011102446314 A CN 2011102446314A CN 201110244631 A CN201110244631 A CN 201110244631A CN 102953138 A CN102953138 A CN 102953138A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- controlled
- polyacrylonitrile
- spun fibre
- manufacture method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a manufacturing method for a polyacrylonitrile-based carbon fiber protofilament. The third monomer of a protofilament spinning raw material polyacrylonitrile resin is itaconic acid. The preparation method comprises the following successive steps: preparing a spinning solution from the resin by using DMSO or DMAc and carrying out spinning and solidification so as to prepare a nascent fiber; placing the nascent fiber in an aqueous solution of the spinning solvent for water bath drafting and carrying out drip washing with deionized water; dipping the nascent fiber in an acidic aqueous solution for 2 to 10 min; then dipping the nascent fiber in a sodium hydroxide or potassium hydroxide aqueous solution for 1 to 5 min; placing the nascent fiber in pure water for water bath drafting; rinsing the nascent fiber with deionized water until rinsing liquid is neutral and sodium or potassium ions cannot be measured, and then continuing rinsing for 5 to 15 min; and carrying out post-processing procedures like oiling and dry densification so as to obtain a product of the polyacrylonitrile-based carbon fiber protofilament. According to the invention, purification of the protofilament is realized through rinsing, and breaking strength of fibers is not affected, so the defects of the prior art are overcome.
Description
Technical field
The present invention relates to make the method for polyacrylonitrile base carbon fiber precursors, particularly take adopt furoate clothing as the polyacrylonitrile resin of the 3rd comonomer as spinning material, make the method for polyacrylonitrile base carbon fiber precursors by the solution spinning technique.
Background technology
Carbon fiber has excellent mechanical property, and other material of the specific strength that it is high and specific modulus hardly matches, and as a kind of reinforcing material, it is widely used in the fields such as manufacturing of space flight, airborne vehicle and sports equipment.Carbon fiber is made after pre-oxidation and carbonization by the precursor that carbonizable substance is made usually, because polyacrylonitrile resin has higher carbonization yield, therefore polyacrylonitrile fibre is ideal carbon fibre precursor, and the carbon fiber that makes is called polyacrylonitrile-based carbon fibre.
Obtain the polyacrylonitrile-based carbon fibre of function admirable, the purifying of precursor is most important, especially higher to the requirement of metals content impurity, such as alkali and alkaline earth metal ions, they carry out the high temperature such as pre-oxidation, carbonization when processing at precursor, thereby the effusion that can promote the gases such as CO, CO2 is at the inner cavity blemish that forms of carbon fiber.If measure metals content impurity in the precursor with ash, precursor is generally considered to be High Purity when ash is lower than 0.1 ‰, and the carbon fiber that makes thus will have higher quality.
Metal species impurity in the polyacrylonitrile base carbon fiber precursors is mainly from the solvent of polymer raw, polymerization initiation system and polymerization or spinning.For the removal of metal impurities can be after last handling process, the precursor of precursor manufacturing be made or the precursor link such as after pre-oxidation adopt the means of washing to carry out, prior art is generally washed with acidic aqueous solution first, carries out rinsing with deionized water again.US Patent No. 3,413,094, US 4,113,847, US 4,507, and 272 have introduced respectively part technology wherein, " pickling of the fine carbon fiber precursor of PAN base and the discussion of ion diffusion mechanism " [" Donghua University's journal (natural science edition) " 06 phase in 1993] literary composition then washs PAN as-spun fibre, finished fiber and pre-oxidized fibers, and the factors such as wash temperature, acid strength, time, stirring and fiber hole have been done detailed elaboration for the relation of clean result etc.At present industrial usually just finishing before pre-oxidation processed the purification impurity elimination of precursor, because metal impurities can damage the structure of preoxided thread when pre-oxidation.
The same with the manufacturing of common acrylic fibers, the spinning material polyacrylonitrile resin of polyacrylonitrile base carbon fiber precursors is not the homopolymers of a kind of monomer polymerization of acrylonitrile, it must contain the second monomer about 2～5wt%, and is commonly used such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate or vinylacetate etc.The existence of the second monomer can destroy the macromolecular regularity of polyacrylonitrile, thereby reduce intermolecular active force the drawing-off of as-spun fibre can be carried out smoothly.In addition, it also contains the 3rd monomer of 0.5～2.0wt%, the most frequently used is itaconic acid, the existence of itaconic acid can change the thermal cyclization reaction behavior of polyacrylonitrile when pre-oxidation, reduce oxidation reaction initial temperature and peak temperature, make the oxidation reaction heat release mild, Wen Fenggeng is wide, oxidizing process is carried out more thoroughly, and this is conducive to improve the mechanical performance of carbon fiber.
Except NaSCN, Zncl
2And HNO
3Deng inorganic salts or aqueous acid as beyond the spin solvent, it is that spin solvent is made with the solution spinning technique that present polyacrylonitrile carbon fiber precursor also more adopts the organic solvents such as dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF) and dimethylacetylamide (DMAc), and wherein the industrial applications of DMSO and DMAc is more general.The purge process of precursor mainly comprises acid solution washing and two steps of rinsing in the prior art, and fiber floods washing to clean the metal impurities in the fiber with acidic aqueous solution first, and is with deionized water that the fiber rinsing is extremely neutral again.It is generally acknowledged to wash before as-spun fibre is not finished drawing-off to have preferably effect, because this moment, fiber was still located gel state, structure is comparatively loose, and the metal ion of fibrous inside easily spreads to cleaning solution.This washing methods is ideal for the effect of removing metal impurities in the fiber, but can bring the drawing-off of fiber unfavorable.This is that polyacrylonitrile macromolecular chain underpants health acid unit is carboxylic acid by the Forms Transformation of carboxylate after cleaning owing to metal impurities are thorough.We know, the hydrogen atom on the carboxylic acid presents positive charge because electronics departs from, and its can form hydrogen bond with the large nitrogen-atoms of electronegativity in the acrylonitrile unit in the strand.This hydrogen bond can be present in makes part segment Cheng Huan in the same macromolecular chain, can also be present between the different large molecules to make adjacent macromolecular part segment crosslinked.Because the adhesion of hydrogen bond is much larger than general intermolecular model Dehua gravitation, this will cause fiber polymer macromolecule when drawing-off to be difficult to be stretched stretching, and the desired result of drawing of fiber is all polymer macromolecules are straightened under the effect of external force and obtain the higher degree of orientation.Experiment shows, under the identical prerequisite of drawing-off multiplying power and other process conditions, and the drawing-off meeting of the as-spun fibre comparatively difficulty that becomes after pickling, the TENSILE STRENGTH of precursor product also presents downward trend, and extension at break is in rising trend simultaneously.Usually the single fiber extension at break rises approximately about 5%, and the lower reduction of filament fracture strength is then more obvious, generally can reach about 15%, and this can have a strong impact on the mechanical performance of carbon fiber finished product undoubtedly.As-spun fibre is finished and is washed that then purification effect is desirable not to the utmost after the drawing-off again, because this moment, fibre structure was comparatively tight, is unfavorable for that metal ion spreads to cleaning solution.Particularly the dissociation constant of alkali earth metal is relatively low, being in the alkaline-earth metal ions that the fiber deep layer exists with the carboxylate form is difficult to be removed by pickling, even strengthen the washing process condition, generally ash still is difficult to reach the level that is lower than 0.1wt ‰ in the precursor product.Up to now, prior art not yet effectively solves purifying and this contradiction of mechanical performance variation of above-mentioned precursor.
Summary of the invention
The invention provides a kind of manufacture method of polyacrylonitrile base carbon fiber precursors, spinning material is the polyacrylonitrile resin of the 3rd comonomer for adopting furoate clothing, and adopts the solution spinning technique take DMSO or DMAc as spin solvent.Technical problem to be solved by this invention is precursor reaches purifying by washing purpose, and fibrous fracture intensity is unaffected simultaneously, thereby remedies the defective that prior art exists.
Below be that the present invention solves the problems of the technologies described above concrete technical scheme:
A kind of manufacture method of polyacrylonitrile base carbon fiber precursors, spinning material polyacrylonitrile resin are the copolymer of three kinds of monomers, and the first monomer is acrylonitrile; The second monomer is taken from a kind of in methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate or the vinylacetate; The 3rd monomer is furoate clothing.The content of the 3rd monomer is 0.5～2.0wt% in the polyacrylonitrile resin, and the total content of the second and the 3rd monomer is 1.0～7.0wt%.
The method may further comprise the steps successively:
1) polyacrylonitrile resin is mixed with spinning solution take DMSO or DMAc as spin solvent, and the aqueous solution of the spin solvent take concentration as 30～50wt% adopts the solution spinning technique as coagulating bath and makes as-spun fibre through spray silk and solidification forming;
2) as-spun fibre carries out the water-bath drawing-off in concentration is the aqueous solution of spin solvent of 20～30wt%, and bath temperature is controlled to be 85～100 ℃, and drafting multiple is controlled to be 3.5～5.0;
3) as-spun fibre deionized water drip washing, water temperature are controlled to be 45～60 ℃, and the drip washing time is controlled to be 2～20min;
4) as-spun fibre places acidic aqueous solution to flood, nitric acid, sulfuric acid or hydrochloric acid are adopted in acid, the pH value of acidic aqueous solution is 2.0～4.0, temperature is controlled to be 45～60 ℃, in weight ratio; bath raio is controlled to be as-spun fibre: solution=1: (15～25), dip time is controlled to be 2～10min;
5) as-spun fibre places NaOH or potassium hydroxide aqueous solution to flood, the concentration of sodium ion in liquor or potassium ion is 200～800mg/L, temperature is controlled to be 40～60 ℃, in weight ratio; bath raio is controlled to be as-spun fibre: solution=1: (5～10), dip time is controlled to be 1～5min;
6) as-spun fibre carries out the water-bath drawing-off in pure water, and bath temperature is controlled to be 95～100 ℃, and drafting multiple is controlled to be 1.3～2.0;
7) the as-spun fibre temperature is that 90～100 ℃ deionized water carries out the hot bath rinsing, continues rinsing 5～15min after rinsing liquid is neutral and does not measure sodium ion or potassium ion again;
8) as-spun fibre is made the polyacrylonitrile base carbon fiber precursors product through last handling process, and last handling process comprises and oiling and compacting by drying.
Above-mentioned steps 4) nitric acid is preferably adopted in described acid; The pH value of acidic aqueous solution is preferably 2.5～3.5; The temperature of acidic aqueous solution is preferably 50～55 ℃; Bath raio preferably is controlled to be as-spun fibre: solution=1: (18～23); Dip time preferably is controlled to be 4～8min.
Above-mentioned steps 5) concentration of described sodium ion in liquor or potassium ion is preferably 300～500mg/L; Solution temperature preferably is controlled to be 45～50 ℃; Bath raio preferably is controlled to be as-spun fibre: solution=1: (6～8); Dip time preferably is controlled to be 3～4min.
As-spun fibre weight can be pressed the pure calculating of polyacrylonitrile resin content in the spinning solution again according to the spinning solution extrusion capacity of spinning part in the bath raio.
Above-mentioned steps 7) the most handy temperature of described as-spun fibre is that 95～98 ℃ deionized water carries out the hot bath rinsing, continues rinsing 7～12min after rinsing liquid is neutral and does not measure sodium ion or potassium ion again.
Same as the prior art, the molecular weight of above-mentioned polyacrylonitrile resin is generally 50000～200000; Above-mentioned steps 1) described polyacrylonitrile resin preferably is mixed with spinning solution take DMSO as spin solvent, and preferably the aqueous solution of the DMSO take concentration as 30～50wt% adopts the solution spinning technique as coagulating bath and makes as-spun fibre through spray silk and solidification forming; Polyacrylonitrile resin content general control is 18～25wt% in the spinning solution.
Essence of the present invention is when as-spun fibre washs the removal metal impurities, and washing process changes a pickling and an alkali lye neutralization into by the general pickling of adopting of prior art, and washing process is positioned at before the drawing-off.As-spun fibre through the washing of acidic aqueous solution dipping, is free on large intermolecular metal impurities and is washed removal under the effect of acid first in the fiber, the furoate clothing unit that exists with the carboxylate form in the large molecule then is converted into carboxylic acid.Then as-spun fibre floods through alkali lye, and the furoate clothing unit that exists with the carboxylic acid form in the large molecule is converted into carboxylic acid sodium salt or sylvite again.As-spun fibre carries out drawing-off immediately, because the nitrogen-atoms of hydrogen atom and acrylonitrile unit on the hydroxy-acid group of furoate clothing unit formation hydrogen bond avoided, and the large molecule of curling the at random orientation that when drawing-off, can successfully be straightened.
As-spun fibre carries out rinsing with deionized water after finishing drawing-off again, because sodium ion or potassium ion have higher dissociation constant, as long as rinsing is abundant, can reach sodium ion or the clean purpose of potassium ion that aqueous slkali is brought into fully with deionized water.The inventor is confirmed by experimental data, and as-spun fibre carries out rinsing by the described process conditions of technical solution of the present invention after finishing drawing-off, and the ash of precursor product all can be lower than 0.1 ‰ basically.
Although it is spin solvent that the present invention only adopts DMSO or DMAc, those skilled in the art is not difficult to know by inference, and other is made polyacrylonitrile fibre organic solvent such as DMF commonly used and is applicable to too the technical program.
Compared with prior art the present invention has obtained substantial progress, and fiber is by washing the satisfactory purpose of removing metal impurities that reached, and purification effect is very good.The drawing-off of fiber then can be smooth, and the filament fracture strength of precursor product can improve about 10～20% relatively, and the single fiber extension at break can reduce about 5～10%, and the invention effect is very obvious.
The invention will be further described below by specific embodiment.Because washing process is main distinction feature of the present invention, spinning material, other spinning and aftertreatment technology etc. are all basic identical with prior art, therefore embodiment and comparative example will be paid attention to enumerating of washing process and draft process condition especially, and show that correspondingly reflection is washed and the testing performance index data of drawing-off effect, such as ash, filament fracture strength and the extension at break of precursor.There are not obvious relevance in other conventional index of precursor and distinguishing characteristics of the present invention, and embodiment and comparative example will it will not go into details.
In embodiment and comparative example, filament fracture strength and extension at break are pressed GB/T 14335-2008 and are measured, and the assay method of ash is seen lower:
Get the sample (quality is m, is accurate to 0.0001g) about 4g, place that (quality is m to constant weight through 800 ℃ of temperature calcinations
0) porcelain crucible in, the crucible that sample is housed is placed on heats 10～30min on the electric furnace, burn to the sample ashing without black smoke.Cooling is put into 800 ℃ high temperature resistance furnace for a moment again on electric furnace, and calcination 2hr makes it ashing, after taking out from high temperature furnace, moves in the drier and is cooled to room temperature, and weighing, (quality is m
1).
Be calculated as follows ash:
The specific embodiment
The spinning material polyacrylonitrile resin that embodiment and comparative example adopt makes by aqueous suspension polymerization technique, second, third comonomer except acrylonitrile is respectively methyl acrylate and itaconic acid, three's weight ratio is 97: 2: 1, and the molecular weight of acrylonitrile resin is 90000.The ash that records the polyacrylonitrile resin raw material is 1.62 ‰.
[embodiment 1～10]
Carry out according to the following steps the preparation of carbon fibre precursor:
1) adopting DMSO is that solvent is mixed with spinning solution with polyacrylonitrile resin, and polyacrylonitrile resin content is 18～25wt% in the spinning solution.Adopt the solution spinning technique to make as-spun fibre through spray silk and solidification forming take the DMSO aqueous solution of 30～50wt% as coagulating bath;
2) as-spun fibre carries out the water-bath drawing-off in the DMSO of the 20～30wt% aqueous solution, and bath temperature and the drafting multiple of each embodiment see Table 1, in the table this step are defined as front draft;
3) as-spun fibre deionized water drip washing, water temperature are controlled to be 45～60 ℃, and the drip washing time is controlled to be 2～20min;
4) as-spun fibre places acidic aqueous solution to flood, and the control data of temperature, bath raio and the dip time etc. of the acid that each embodiment acidic aqueous solution adopts and pH value, acidic aqueous solution see Table 2;
5) as-spun fibre places NaOH or potassium hydroxide aqueous solution to flood, and the control data of temperature, bath raio and the dip time etc. of the alkali that each embodiment alkaline aqueous solution adopts and the concentration of sodium ion in liquor or potassium ion, alkaline aqueous solution see Table 3;
6) as-spun fibre carries out the water-bath drawing-off in pure water, and the control data of each embodiment bath temperature and drafting multiple see Table 1, in the table this step are defined as first break draft;
7) as-spun fibre carries out the hot bath rinsing with deionized water, and when the continuation rinsing was counted after being neutral and not measuring sodium ion or potassium ion to rinsing liquid, the temperature of each embodiment hot bath, continuation rinsing time and total rinsing time saw Table 4;
8) as-spun fibre is through oiling and the last handling process such as compacting by drying, and obtaining fiber number is the polyacrylonitrile base carbon fiber precursors product of 1.22dtex.
[embodiment 11～12]
Carry out according to the following steps the preparation of carbon fibre precursor:
1) adopting DMAc is that solvent is mixed with spinning solution with polyacrylonitrile resin, and polyacrylonitrile resin content is 18～25wt% in the spinning solution.Adopt the solution spinning technique to make as-spun fibre through spray silk and solidification forming take the DMAc aqueous solution of 30～50wt% as coagulating bath;
2)～8) identical with embodiment 1～10.
[comparative example 1～4]
Carry out according to the following steps the preparation of carbon fibre precursor:
1)～3) identical with embodiment 1～10, each comparative example step 2) bath temperature and drafting multiple see Table 1;
4) as-spun fibre places acidic aqueous solution to flood, and the control data of acid, pH value, temperature, bath raio and dip time etc. that each comparative example acidic aqueous solution adopts see Table 2;
5) as-spun fibre carries out the hot bath rinsing with deionized water, is neutral to rinsing liquid, and temperature and the rinsing time of each comparative example hot bath see Table 4;
6) as-spun fibre carries out the water-bath drawing-off in pure water, and the control data of each comparative example bath temperature and drafting multiple see Table 1, in the table this step are defined as first break draft;
7) as-spun fibre is through oiling and the last handling process such as compacting by drying, and obtaining fiber number is the polyacrylonitrile base carbon fiber precursors product of 1.22dtex.
Test ash, filament fracture strength and the extension at break of each embodiment and comparative example precursor product, the results are shown in Table 5.
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Claims (14)
1. the manufacture method of a polyacrylonitrile base carbon fiber precursors, the spinning material polyacrylonitrile resin is the copolymer of three kinds of monomers, the first monomer is acrylonitrile; The second monomer is taken from a kind of in methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate or the vinylacetate; The 3rd monomer is furoate clothing, and the content of the 3rd monomer is 0.5～2.0wt% in the polyacrylonitrile resin, and the total content of the second and the 3rd monomer is 1.0～7.0wt%, it is characterized in that the method may further comprise the steps successively:
1) polyacrylonitrile resin is mixed with spinning solution take DMSO or DMAc as spin solvent, and the aqueous solution of the spin solvent take concentration as 30～50wt% adopts the solution spinning technique as coagulating bath and makes as-spun fibre through spray silk and solidification forming;
2) as-spun fibre carries out the water-bath drawing-off in concentration is the aqueous solution of spin solvent of 20～30wt%, and bath temperature is controlled to be 85～100 ℃, and drafting multiple is controlled to be 3.5～5.0;
3) as-spun fibre deionized water drip washing, water temperature are controlled to be 45～60 ℃, and the drip washing time is controlled to be 2～20min;
4) as-spun fibre places acidic aqueous solution to flood, nitric acid, sulfuric acid or hydrochloric acid are adopted in acid, the pH value of acidic aqueous solution is 2.0～4.0, temperature is controlled to be 45～60 ℃, in weight ratio; bath raio is controlled to be as-spun fibre: solution=1: (15～25), dip time is controlled to be 2～10min;
5) as-spun fibre places NaOH or potassium hydroxide aqueous solution to flood, the concentration of sodium ion in liquor or potassium ion is 200～800mg/L, temperature is controlled to be 40～60 ℃, in weight ratio; bath raio is controlled to be as-spun fibre: solution=1: (5～10), dip time is controlled to be 1～5min;
6) as-spun fibre carries out the water-bath drawing-off in pure water, and bath temperature is controlled to be 95～100 ℃, and drafting multiple is controlled to be 1.3～2.0;
7) the as-spun fibre temperature is that 90～100 ℃ deionized water carries out the hot bath rinsing, continues rinsing 5～15min after rinsing liquid is neutral and does not measure sodium ion or potassium ion again;
8) as-spun fibre is made the polyacrylonitrile base carbon fiber precursors product through last handling process, and last handling process comprises and oiling and compacting by drying.
2. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that step 4) described acid employing nitric acid.
3. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that step 4) the pH value of described acidic aqueous solution is 2.5～3.5.
4. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that step 4) temperature of described acidic aqueous solution is 50～55 ℃.
5. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that step 4) described bath raio is controlled to be as-spun fibre: solution=1: (18～23).
6. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that step 4) described dip time is controlled to be 4～8min.
7. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that step 5) concentration of described sodium ion in liquor or potassium ion is 300～500mg/L.
8. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that step 5) described solution temperature is controlled to be 45～50 ℃.
9. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that step 5) described bath raio is controlled to be as-spun fibre: solution=1: (6～8).
10. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that step 5) described dip time is controlled to be 3～4min.
11. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterized in that step 7) described as-spun fibre temperature is that 95～98 ℃ deionized water carries out the hot bath rinsing, continues rinsing 7～12min after rinsing liquid is neutral and does not measure sodium ion or potassium ion again.
12. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1, the molecular weight that it is characterized in that described polyacrylonitrile resin is 50000～200000.
13. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterized in that step 1) described polyacrylonitrile resin is mixed with spinning solution take DMSO as spin solvent, and the aqueous solution of the DMSO take concentration as 30～50wt% adopts the solution spinning technique as coagulating bath and makes as-spun fibre through spray silk and solidification forming.
14. the manufacture method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that step 1) polyacrylonitrile resin content is 18～25wt% in the described spinning solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110244631.4A CN102953138B (en) | 2011-08-25 | 2011-08-25 | A kind of manufacture method of polyacrylonitrile base carbon fiber precursors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110244631.4A CN102953138B (en) | 2011-08-25 | 2011-08-25 | A kind of manufacture method of polyacrylonitrile base carbon fiber precursors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102953138A true CN102953138A (en) | 2013-03-06 |
| CN102953138B CN102953138B (en) | 2016-01-20 |
Family
ID=47762501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110244631.4A Active CN102953138B (en) | 2011-08-25 | 2011-08-25 | A kind of manufacture method of polyacrylonitrile base carbon fiber precursors |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102953138B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103726113A (en) * | 2013-12-25 | 2014-04-16 | 中国科学院化学研究所 | Novel fiber-drawing hot bath medium and application thereof |
| CN104371060A (en) * | 2013-08-13 | 2015-02-25 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile resin with evenly-distributed copolymerization sequence |
| CN106637519A (en) * | 2016-11-29 | 2017-05-10 | 江西师范大学 | Preparation method of oleic acid/acrylonitrile copolymer based carbon fiber |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3413094A (en) * | 1966-01-24 | 1968-11-26 | Hitco | Method of decreasing the metallic impurities of fibrous carbon products |
| US4113847A (en) * | 1975-09-01 | 1978-09-12 | Japan Exlan Company Limited | Process for producing carbon fibers |
| US4388289A (en) * | 1977-05-26 | 1983-06-14 | Hitco | Method of removing alkali and alkaline earth metal impurities from oxidized pan material |
| US4507272A (en) * | 1983-05-09 | 1985-03-26 | Hitco | Method of purifying partially carbonized pan material prior to carbonization |
| 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 |
| 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 |
| CN101643943A (en) * | 2009-07-10 | 2010-02-10 | 东华大学 | Preparation method for polyacrylonitrile-based carbon fiber protofilament |
| CN101724922A (en) * | 2009-11-26 | 2010-06-09 | 中复神鹰碳纤维有限责任公司 | Method for preparing high-strength polyacrylonitrile-based precursor for carbon fiber |
-
2011
- 2011-08-25 CN CN201110244631.4A patent/CN102953138B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3413094A (en) * | 1966-01-24 | 1968-11-26 | Hitco | Method of decreasing the metallic impurities of fibrous carbon products |
| US4113847A (en) * | 1975-09-01 | 1978-09-12 | Japan Exlan Company Limited | Process for producing carbon fibers |
| US4388289A (en) * | 1977-05-26 | 1983-06-14 | Hitco | Method of removing alkali and alkaline earth metal impurities from oxidized pan material |
| US4507272A (en) * | 1983-05-09 | 1985-03-26 | Hitco | Method of purifying partially carbonized pan material prior to carbonization |
| 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 |
| 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 |
| CN101643943A (en) * | 2009-07-10 | 2010-02-10 | 东华大学 | Preparation method for polyacrylonitrile-based carbon fiber protofilament |
| CN101724922A (en) * | 2009-11-26 | 2010-06-09 | 中复神鹰碳纤维有限责任公司 | Method for preparing high-strength polyacrylonitrile-based precursor for carbon fiber |
Non-Patent Citations (1)
| Title |
|---|
| 于淑娟: "《碳纤维用聚丙烯腈原丝制备技术的研究进展》", 《高科技纤维与应用》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371060A (en) * | 2013-08-13 | 2015-02-25 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile resin with evenly-distributed copolymerization sequence |
| CN103726113A (en) * | 2013-12-25 | 2014-04-16 | 中国科学院化学研究所 | Novel fiber-drawing hot bath medium and application thereof |
| CN106637519A (en) * | 2016-11-29 | 2017-05-10 | 江西师范大学 | Preparation method of oleic acid/acrylonitrile copolymer based carbon fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102953138B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100557098C (en) | A kind of manufacture method of polyacrylonitrile base carbon fiber precursors | |
| CN102953153B (en) | A kind of preparation method of polyacrylonitrile-based carbon fibre | |
| CN100570026C (en) | The manufacture method of polyacrylonitrile base carbon fiber precursors | |
| CN102517671B (en) | Method for preparing carbon fiber precursor by two-step process of aqueous suspension and solution polymerization | |
| JP5656185B2 (en) | Method for producing flame-resistant acrylonitrile polymer | |
| CN102953151A (en) | Preparation method for polyacrylonitrile-based carbon fiber | |
| CN103233297A (en) | 6k polyacrylonitrile-based carbon fibre manufacturing method | |
| CN103952797A (en) | Preparation method of wet-process high-strength polyacrylonitrile-based carbon fiber | |
| CN102953138B (en) | A kind of manufacture method of polyacrylonitrile base carbon fiber precursors | |
| CN102953141A (en) | Manufacturing method for polyacrylonitrile-based carbon fiber protofilament | |
| CN102953139B (en) | The preparation method of polyacrylonitrile base carbon fiber precursors | |
| CN103614800B (en) | A kind of preparation method of binary polyacrylonitrile base carbon fiber precursors | |
| CN102953158A (en) | Manufacturing method for polyacrylonitrile-based carbon fiber | |
| CN102953156A (en) | Manufacturing method for polyacrylonitrile-based carbon fiber | |
| CN102953144A (en) | Preparation method for polyacrylonitrile-based carbon fiber protofilament | |
| CN102953142A (en) | Manufacturing method for polyacrylonitrile-based carbon fiber protofilament | |
| CN102953154A (en) | Manufacturing method for polyacrylonitrile-based carbon fiber | |
| CN102953140A (en) | Preparation method for polyacrylonitrile-based carbon fiber protofilament | |
| CN102953145A (en) | Preparation method for polyacrylonitrile-based carbon fiber protofilament | |
| CN102953140B (en) | Polyacrylonitrile base carbon fiber precursors preparation method | |
| CN102953157B (en) | The preparation method of polyacrylonitrile-based carbon fibre | |
| CN102953143A (en) | Preparation method for polyacrylonitrile-based carbon fiber protofilament | |
| CN102953155A (en) | Preparation method for polyacrylonitrile-based carbon fiber | |
| CN102953152A (en) | Preparation method for polyacrylonitrile-based carbon fiber | |
| KR101909892B1 (en) | The method of producing the polyacrylonitrile precursor for carbon fiber and the method of producing carbon fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |