CN102953142B - A kind of method manufacturing polyacrylonitrile base carbon fiber precursors - Google Patents
A kind of method manufacturing polyacrylonitrile base carbon fiber precursors Download PDFInfo
- Publication number
- CN102953142B CN102953142B CN201110244662.XA CN201110244662A CN102953142B CN 102953142 B CN102953142 B CN 102953142B CN 201110244662 A CN201110244662 A CN 201110244662A CN 102953142 B CN102953142 B CN 102953142B
- Authority
- CN
- China
- Prior art keywords
- spun fibre
- aqueous solution
- carbon fiber
- bath
- controls
- 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.)
- Active
Links
Landscapes
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
A kind of method manufacturing polyacrylonitrile base carbon fiber precursors, spinning material polyacrylonitrile resin Third monomer is furoate clothing, includes successively: resin NaSCN solution becomes spinning solution to prepare as-spun fibre through spray webbing and solidification forming；As-spun fibre carries out water-bath drawing-off and through deionized water drip washing in NaSCN aqueous solution；As-spun fibre is placed in acidic aqueous solution and impregnates；As-spun fibre is placed in sodium hydroxide or potassium hydroxide aqueous solution and impregnates；As-spun fibre carries out water-bath drawing-off in pure water and rinses through hot bath, is further continued for rinsing 5～15min to rinsing liquid in neutrality and after not measuring sodium ion or potassium ion；Through oiling and the last handling process such as compacting by drying makes polyacrylonitrile base carbon fiber precursors product.Having reached the purpose of precursor purification after scrubbed, fibrous fracture intensity is unaffected simultaneously, thus compensate for the defect that prior art exists.
Description
Technical field
The present invention relates to the method manufacturing polyacrylonitrile base carbon fiber precursors, particularly to adopt furoate clothing for the polyacrylonitrile resin of the 3rd comonomer as spinning material, by the method that solution spinning processes manufactures polyacrylonitrile base carbon fiber precursors.
Background technology
Carbon fiber has the mechanical property of excellence, and its high specific strength and other material of specific modulus hardly match, and as a kind of reinforcing material, it is widely used in the field such as manufacture of space flight, airborne vehicle and sports equipment.The precursor that carbon fiber is generally made up of carbonizable substance prepares after pre-oxidation and carbonization, and owing to polyacrylonitrile resin has higher carbonization yield, therefore polyacrylonitrile fibre is ideal carbon fibre precursor, and prepared carbon fiber is called polyacrylonitrile-based carbon fibre.
Obtain the polyacrylonitrile-based carbon fibre of function admirable, the purification of precursor is most important, especially the requirement of metals content impurity is higher, such as alkali and alkaline earth metal ions, they, when precursor carries out the high-temperature process such as pre-oxidation, carbonization, can promote the effusion of the gases such as CO, CO2 thus being internally formed cavity blemish at carbon fiber.If measuring metals content impurity in precursor with ash, when ash is lower than 0.1 ‰, precursor is generally considered to be High Purity, and the carbon fiber thus prepared will have higher quality.
Metal class impurity in polyacrylonitrile base carbon fiber precursors is essentially from the solvent of polymer raw, polymerization initiation system and polymerization or spinning.For metal impurities removal can after the last handling process of precursor manufacture, precursor are made or the precursor link such as after pre-oxidation adopt the means of washing to carry out, prior art is generally first washed with acidic aqueous solution, then rinses with deionized water.US Patent No. 3,413,094, US4,113,847, US4,507,272 portion of techniques therein is described respectively, " pickling of PAN base fibre carbon fiber precursor and the discussion of ion diffusion mechanism " [" Donghua University's journal (natural science edition) " 06 phase in 1993], PAN as-spun fibre, finished fiber and pre-oxidized fibers were then washed by a literary composition, and the factor such as wash temperature, acid strength, time, stirring and fiber hole has done detailed elaboration for the relation etc. of clean result.The structure of preoxided thread current industrial generally before pre-oxidation, just complete the purification roguing to precursor and processes, because can be damaged when pre-oxidation by metal impurities.
Manufacture with common acrylon is the same, the spinning material polyacrylonitrile resin of polyacrylonitrile base carbon fiber precursors is not the homopolymer of a kind of monomer polymerization of acrylonitrile, it must contain the second comonomer of about 2～5wt%, conventional such as acrylic acid methyl ester., ethyl acrylate, methyl methacrylate, ethyl methacrylate or vinylacetate etc..The existence of second comonomer can destroy the regularity of polyacrylonitrile macromole, reduces intermolecular active force so that the drawing-off of as-spun fibre can be smoothed out.In addition, it is possibly together with the Third monomer of 0.5～2.0wt%, the most frequently used is itaconic acid, the existence in itaconic acid can change the polyacrylonitrile thermal cyclization reaction behavior when pre-oxidation, reducing oxidation reaction initial temperature and peak temperature, make oxidation reaction heat release mild, temperature peak is wider, oxidizing process carries out more thorough, this mechanical performance being conducive to improving carbon fiber.
Current polyacrylonitrile carbon fiber precursor still more adopts inorganic salt or aqueous acid to be solvent spinning technique manufacture in a wet process, and conventional inorganic salt or acid include NaSCN, Zncl2And HNO3Deng, wherein the industrial applications of NaSCN is the most general.In prior art, the purge process of precursor mainly includes acid solution washing and two steps of rinsing, and fiber first carries out dipping washing with the metal impurities in clean fiber with acidic aqueous solution, then rinses fiber to neutral with deionized water.It is generally acknowledged that carrying out washing before as-spun fibre is not fully complete drawing-off has good effect, because now gel state still located by fiber, structure is comparatively loose, and the metal ion of fibrous inside easily spreads to cleaning mixture.This washing methods is ideal for removing the effect of metal impurities in fiber, but the drawing-off of fiber can be brought unfavorable.This is after thoroughly cleaning due to metal impurities, and 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 it can be big with electronegativity in acrylonitrile unit in strand forms hydrogen bond.This hydrogen bond may be present in and makes moiety segments cyclization in same macromolecular chain, can exist in the moiety segments crosslinking of the adjacent macromole of chien shih of different macromole.Owing to the adhesion of hydrogen bond is much larger than general intermolecular model Dehua gravitation, this will cause that fiber polymer macromolecule when drawing-off is difficult to be extended and stretch, 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 higher degree of orientation.Experiments show that, under the premise that draft ratio and other process conditions are identical, after pickling, the drawing-off of as-spun fibre can become comparatively difficulty, and the hot strength of precursor product also presents downward trend, and extension at break is in rising trend simultaneously.Usual single fiber extension at break rises about about 5%, and the lower reduction of broken filament intensity then becomes apparent from, and generally up to about 15%, this can have a strong impact on the mechanical performance of carbon fiber finished product undoubtedly.As-spun fibre carries out washing then purification effect again after completing drawing-off desirable not to the utmost, because now fibre structure is comparatively tight, is unfavorable for that metal ion spreads to cleaning mixture.Particularly the ionization constant of alkali earth metal is relatively low, it is in Fibrous depth to be difficult to be removed by pickling with the alkaline-earth metal ions that carboxylate form exists, even if strengthening washing process condition, in precursor product, ash is still difficult to reach the level lower than 0.1wt ‰ under normal circumstances.Up to now, prior art not yet effectively solves purification and this contradiction of mechanical degradation of above-mentioned precursor.
Summary of the invention
The invention provides a kind of method manufacturing polyacrylonitrile base carbon fiber precursors, spinning material is the polyacrylonitrile resin adopting furoate clothing to be the 3rd comonomer, and adopts NaSCN aqueous solution wet spinning technology.The technical problem to be solved is the purpose being reached purification by precursor washing, and fibrous fracture intensity is unaffected simultaneously, thus making up the defect that prior art exists.
The following is the technical scheme that this invention address that above-mentioned technical problem is concrete:
A kind of method manufacturing polyacrylonitrile base carbon fiber precursors, spinning material polyacrylonitrile resin is the copolymer of three kinds of monomers, and the first monomer is acrylonitrile；Second comonomer takes from the one in acrylic acid methyl ester., ethyl acrylate, methyl methacrylate, ethyl methacrylate 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 the NaSCN aqueous solution of 45～58wt% for solvent, adopts wet spinning technology to prepare as-spun fibre through spray webbing and solidification forming with the NaSCN aqueous solution of 8～16wt% for coagulating bath；
2) as-spun fibre carries out water-bath drawing-off in the NaSCN aqueous solution of 1～5wt%, and it is 5～30 DEG C that bath temperature controls, and it is 1.5～2.5 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 acidic aqueous solution and impregnates, acid adopts sulphuric acid, hydrochloric acid or nitric acid, the pH value of acidic aqueous solution is 0.5～3.0, it is 45～60 DEG C that temperature controls, with mass ratio range; bath raio controls as as-spun fibre: solution=1: (15～25), it is 2～15min that dip time controls；
5) as-spun fibre is placed in sodium hydroxide or potassium hydroxide aqueous solution and impregnates, the concentration of sodium ion in liquor or potassium ion is 200～800mg/L, it is 40～60 DEG C that temperature controls, 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 it is 3～5 that drafting multiple controls；
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 be further continued for rinsing 5～15min after not measuring sodium ion or potassium ion；
8) the post-treated process of as-spun fibre makes polyacrylonitrile base carbon fiber precursors product, and last handling process includes oiling and compacting by drying.
Above-mentioned steps 4) described in acid preferably with nitric acid；The pH value of acidic aqueous solution is preferably 1.0～2.0；The temperature of acidic aqueous solution is preferably 50～55 DEG C；Bath raio preferably controls as as-spun fibre: solution=1: (18～23)；Dip time preferably controls to be 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 controls to be 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 the pure calculating of polyacrylonitrile resin content in spinning solution again according to the spinning solution extrusion capacity of spinning part.
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, to rinsing liquid in neutral and be further continued for rinsing 7～12min 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 in spinning solution in polyacrylonitrile resin content general control be 10～14wt%.
The essence of the present invention is that the pickling that washing process is generally adopted by prior art changes a pickling into and an alkali liquor neutralizes, before washing process is positioned at drawing-off when as-spun fibre carries out washing removal metal impurities.As-spun fibre is first through acidic aqueous solution dipping washing, and the metal impurities being free between macromole in fiber are washed to remove under the action of an acid, and the furoate clothing unit existed with carboxylate form in macromole is then converted into carboxylic acid.Then the furoate clothing unit that as-spun fibre exists with carboxylic acid form in soda-dip, macromole is then converted to carboxylic acid sodium salt or potassium salt.As-spun fibre carries out drawing-off immediately, is avoided by owing to the nitrogen-atoms of the hydrogen atom on the hydroxy-acid group of furoate clothing unit and acrylonitrile unit forms hydrogen bond, and the macromole curled at random 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 ionization constant, as long as rinsing is fully, is fully able to the sodium ion reaching to be brought into by aqueous slkali with deionized water or purpose that potassium ion is cleaned.Inventor is confirmed by experimental data, and as-spun fibre rinses by the process conditions described in technical solution of the present invention after completing drawing-off, and the ash of precursor product substantially all can lower than 0.1 ‰.
Although the present invention is spin solvent only with NaSCN aqueous solution, but those skilled in the art is not difficult to know by inference, and other manufactures the inorganic solvent such as HN0 that polyacrylonitrile fibre is conventional3、Zncl2Etc. being applied equally to the technical program.
Compared with prior art the present invention achieves substantial progress, and fiber is by washing the satisfactory purpose having reached to remove metal impurities, and purification effect is very good.The drawing-off of fiber then can be smooth, and the broken filament intensity of precursor product can improve about 10～20% relatively, and single fiber extension at break can reduce about 5～10%, and invention effect is extremely obvious.
Below by specific embodiment, the invention will be further described.Owing to washing process is the main distinguishing feature of the present invention, spinning material, other spinning and aftertreatment technology etc. are all essentially identical with prior art, therefore embodiment and comparative example will focus on enumerating of washing process and draft process condition, and correspondingly show that the testing performance index data with drawing-off effect are washed in reflection, such as the ash of precursor, broken filament intensity and extension at break.Other conventional index of precursor and distinguishing feature of the present invention are absent from obvious relatedness, embodiment and comparative example by it will not go into details.
In embodiment and comparative example, broken filament intensity and extension at break are pressed GB/T14335-2008 and are measured, under the assay method of ash is shown in:
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 that (quality is m0) porcelain crucible in, will be equipped with the crucible of sample and be placed on electric furnace heating 10～30min, burn to sample ashing without black smoke.On electric furnace, in cooling a moment, place in the high temperature resistance furnace of 800 DEG C, and calcination 2hr, so as to ashing, after taking out, moves in exsiccator and is cooled to room temperature from high temperature furnace, and 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 adopt is prepared by aqueous suspension polymerization technique, second, third comonomer respectively acrylic acid methyl ester. except acrylonitrile and itaconic acid, the weight ratio of three is 97: 2: 1, and the molecular weight of acrylonitrile resin is 90000.The ash recording polyacrylonitrile resin raw material is 1.62 ‰.
[embodiment 1～12]
Carry out the preparation of carbon fibre precursor according to the following steps:
1) polyacrylonitrile resin is configured to spinning solution with the NaSCN aqueous solution of 45～58wt% for solvent, and in spinning solution, polyacrylonitrile resin content is 10～14wt%.Wet spinning technology is adopted to prepare as-spun fibre through spray webbing and solidification forming with the NaSCN aqueous solution of 8～16wt% for coagulating bath；
2) as-spun fibre carries out water-bath drawing-off, the bath temperature of each embodiment and drafting multiple in Table 1 in the NaSCN aqueous solution of 1～5wt%, 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 acidic aqueous solution and impregnates, and the acid of each embodiment acidic aqueous solution employing and the control data of pH value, the temperature of acidic aqueous solution, bath raio and dip time etc. are in Table 2；
5) as-spun fibre is placed in sodium hydroxide or potassium hydroxide aqueous solution and impregnates, and the alkali of each embodiment alkaline aqueous solution employing and the control data of sodium ion in liquor or the concentration of potassium ion, the temperature of alkaline aqueous solution, bath raio and dip time etc. are in Table 3；
6) as-spun fibre carries out water-bath drawing-off in pure water, and this step, in Table 1, is defined as first break draft in table by the control data of each embodiment bath temperature and drafting multiple；
7) as-spun fibre deionized water carries out hot bath rinsing, and when continuing rinsing number after being neutral to rinsing liquid and do not measure sodium ion or potassium ion, the temperature of each embodiment hot bath, continuation rinsing time and total rinsing time are in Table 4；
8) as-spun fibre is through oiling and the last handling process such as compacting by drying, obtains the polyacrylonitrile base carbon fiber precursors product that fiber number is 1.22dtex.
[comparative example 1～4]
Carry out the preparation of carbon fibre precursor according to the following steps:
1)～3) with embodiment 1～12 identical, each comparative example step 2) bath temperature and drafting multiple in Table 1；
4) as-spun fibre is placed in acidic aqueous solution and impregnates, and the control data of acid, pH value, temperature, bath raio and dip time etc. that each comparative example acidic aqueous solution adopts are in Table 2；
5) as-spun fibre deionized water carries out hot bath rinsing, and to rinsing liquid in neutrality, the temperature of each comparative example hot bath and rinsing time are in Table 4；
6) as-spun fibre carries out water-bath drawing-off in pure water, and this step, in Table 1, is defined as first break draft in table by the control data of each comparative example bath temperature and drafting multiple；
7) as-spun fibre is through oiling and the last handling process such as compacting by drying, obtains the polyacrylonitrile base carbon fiber precursors product that fiber number is 1.22dtex.
Testing each embodiment and the ash of comparative example precursor product, broken filament intensity and extension at break, result is in Table 5.
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Claims (4)
1. the method manufacturing polyacrylonitrile base carbon fiber precursors, spinning material polyacrylonitrile resin is the copolymer of three kinds of monomers, and the first monomer is acrylonitrile；Second comonomer takes from acrylic acid methyl ester.；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 the method comprises the following steps successively:
1) polyacrylonitrile resin is configured to spinning solution with the NaSCN aqueous solution of 45～58wt% for solvent, adopts wet spinning technology to prepare as-spun fibre through spray webbing and solidification forming with the NaSCN aqueous solution of 8～16wt% for coagulating bath；
2) as-spun fibre carries out water-bath drawing-off in the NaSCN aqueous solution of 1～5wt%, and it is 5～30 DEG C that bath temperature controls, and it is 1.5～2.5 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 acidic aqueous solution and impregnates, acid adopts sulphuric acid, hydrochloric acid or nitric acid, the pH value of acidic aqueous solution is 0.5～3.0, it is 45～60 DEG C that temperature controls, with mass ratio range; bath raio controls as as-spun fibre: solution=1: (15～25), it is 2～15min that dip time controls；
5) as-spun fibre is placed in sodium hydroxide or potassium hydroxide aqueous solution and impregnates, the concentration of sodium ion in liquor or potassium ion is 200～800mg/L, it is 40～60 DEG C that temperature controls, 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 it is 3～5 that drafting multiple controls；
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 be further continued for rinsing 5～15min after not measuring sodium ion or potassium ion；
8) the post-treated process of as-spun fibre makes polyacrylonitrile base carbon fiber precursors product, and last handling process includes oiling and compacting by drying.
2. the method for manufacture polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterised in that step 4) described in acid adopt nitric acid.
3. the method for manufacture polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterised in that step 4) described in the pH value of acidic aqueous solution be 1.0～2.0.
4. the method for manufacture polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterised in that step 4) described in the temperature of acidic aqueous solution be 50～55 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110244662.XA CN102953142B (en) | 2011-08-25 | 2011-08-25 | A kind of method manufacturing polyacrylonitrile base carbon fiber precursors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110244662.XA CN102953142B (en) | 2011-08-25 | 2011-08-25 | A kind of method manufacturing polyacrylonitrile base carbon fiber precursors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102953142A CN102953142A (en) | 2013-03-06 |
| CN102953142B true CN102953142B (en) | 2016-06-29 |
Family
ID=47762505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110244662.XA Active CN102953142B (en) | 2011-08-25 | 2011-08-25 | A kind of method manufacturing polyacrylonitrile base carbon fiber precursors |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102953142B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109023593A (en) * | 2018-06-05 | 2018-12-18 | 中国石油化工股份有限公司 | The method for improving sodium sulfocyanate legal system polyacrylonitrile carbon fiber performance |
Citations (4)
| 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 |
| JPS63203821A (en) * | 1987-02-17 | 1988-08-23 | Mitsubishi Rayon Co Ltd | Production of molded article of heat-resistant and flame-retardant acrylic fiber |
| CN101161880A (en) * | 2007-11-22 | 2008-04-16 | 吉林奇峰化纤股份有限公司 | Method for preparing polyacrylonitrile-based carbon fiber precursor fiber |
| 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 |
-
2011
- 2011-08-25 CN CN201110244662.XA patent/CN102953142B/en active Active
Patent Citations (4)
| 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 |
| JPS63203821A (en) * | 1987-02-17 | 1988-08-23 | Mitsubishi Rayon Co Ltd | Production of molded article of heat-resistant and flame-retardant acrylic fiber |
| 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 |
| CN101161880A (en) * | 2007-11-22 | 2008-04-16 | 吉林奇峰化纤股份有限公司 | Method for preparing polyacrylonitrile-based carbon fiber precursor fiber |
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》;20031231;第28卷(第06期);15-18 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102953142A (en) | 2013-03-06 |
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 | |
| JP5656185B2 (en) | Method for producing flame-resistant acrylonitrile polymer | |
| JP2016540131A (en) | Polyacrylonitrile-based precursor fiber for carbon fiber and method for producing the same | |
| WO1999010572A1 (en) | Acrylonitrile-based precursor fiber for carbon fiber, process for producing the same, and carbon fiber obtained from the precursor fiber | |
| CN104630937A (en) | Polyacrylonitrile (PAN)-based high-strength and high-modulus carbon fiber | |
| CN102953151A (en) | Preparation method for polyacrylonitrile-based carbon fiber | |
| CN102953138B (en) | A kind of manufacture method of polyacrylonitrile base carbon fiber precursors | |
| CN102953139B (en) | The preparation method of polyacrylonitrile base carbon fiber precursors | |
| CN102953142B (en) | A kind of method manufacturing polyacrylonitrile base carbon fiber precursors | |
| CN102953141A (en) | Manufacturing method for polyacrylonitrile-based carbon fiber protofilament | |
| CN102953158B (en) | A kind of method of manufacture polyacrylonitrile-based carbon fibre | |
| CN102953143B (en) | A kind of preparation method of polyacrylonitrile base carbon fiber precursors | |
| CN102953154B (en) | A kind of manufacture method of polyacrylonitrile-based carbon fibre | |
| CN102953156A (en) | Manufacturing method for polyacrylonitrile-based carbon fiber | |
| CN102953140B (en) | Polyacrylonitrile base carbon fiber precursors preparation method | |
| CN102953145B (en) | The method preparing polyacrylonitrile base carbon fiber precursors | |
| CN102953157B (en) | The preparation method of polyacrylonitrile-based carbon fibre | |
| CN102953155B (en) | Polyacrylonitrile-based carbon fibre preparation method | |
| CN102953144A (en) | Preparation method for polyacrylonitrile-based carbon fiber protofilament | |
| CN102953152B (en) | Preparation method for polyacrylonitrile-based carbon fiber | |
| CN102953140A (en) | Preparation method for polyacrylonitrile-based carbon fiber protofilament | |
| CN102953155A (en) | Preparation method for polyacrylonitrile-based carbon fiber | |
| JP3073580B2 (en) | Acrylonitrile-based carbon fiber and method for producing the same |
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 |