CN85103318A - Multi-component polyacrylonitrile raw filment for carbon fiber - Google Patents
Multi-component polyacrylonitrile raw filment for carbon fiber Download PDFInfo
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- CN85103318A CN85103318A CN85103318.0A CN85103318A CN85103318A CN 85103318 A CN85103318 A CN 85103318A CN 85103318 A CN85103318 A CN 85103318A CN 85103318 A CN85103318 A CN 85103318A
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- carbon fiber
- acrylonitrile
- methyl acrylate
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 20
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000007062 hydrolysis Effects 0.000 claims abstract description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 17
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000009987 spinning Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 238000009825 accumulation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000013522 chelant Substances 0.000 claims 1
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 claims 1
- 238000002166 wet spinning Methods 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 7
- 125000003368 amide group Chemical group 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 125000004185 ester group Chemical group 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010304 firing Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- SWUMLOXBPGDJOR-UHFFFAOYSA-N 2-methylidenebutanedioic acid;prop-2-enenitrile Chemical compound C=CC#N.OC(=O)CC(=C)C(O)=O SWUMLOXBPGDJOR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- YHBMTHAEQRHTGJ-UHFFFAOYSA-N 2-methylidenebutanedioic acid;methyl prop-2-enoate;prop-2-enenitrile Chemical compound C=CC#N.COC(=O)C=C.OC(=O)CC(=C)C(O)=O YHBMTHAEQRHTGJ-UHFFFAOYSA-N 0.000 description 1
- 101100493705 Caenorhabditis elegans bath-36 gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012660 binary copolymerization Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- -1 dicarbonyl compound Chemical class 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Artificial Filaments (AREA)
- Inorganic Fibers (AREA)
Abstract
The present invention is that acrylonitrile is dissolved in and carries out homogeneous polymerization in 67% aqueous solution of nitric acid with a small amount of methyl acrylate, methylene succinic acid, and the control cyan-hydrolysis is an amide groups, hydrolysis of ester group is a carboxyl, form the viscosity solution of multicomponent mixture polymer, through the wet moulding of specified conditions obtain that homogeneity is good, that thermal behavior is stable, the manufacture method of mild, that preoxidation time is short, the precursor that is suitable for firing high strong type carbon fiber of heat release in the pre-oxidation.
The present invention has also announced the composition and the physical and mechanical properties of the multi-component polyacrylonitrile raw filment for carbon fiber that makes with the method.
Description
To be acrylonitrile with a small amount of other monomers be dissolved in carries out homogeneous polymerization in the aqueous solution of nitric acid in the present invention, and the control cyan-hydrolysis is that amide groups, hydrolysis of ester group are the viscosity solution that carboxyl forms polynary component polymer, through the wet-formed manufacture method that is applicable to the precursor of firing high strong type carbon fiber that obtains of specified conditions.
The polymerization initiator that Japan special permission 43-29593 proposes to adopt peroxide and dicarbonyl compound and slaine to form carry out acrylonitrile in 55～68% aqueous solution of nitric acid under-15～15 ℃ of temperature polymerization make the method for polyacryl-nitrile spinning fluid, this method declares not exist the hydrolysis of cyano group, its shortcoming is that polymerization time is longer, polymerization system is dangerous, and the possibility of blasting is arranged.
We are for overcoming above-mentioned shortcoming by researching and proposing:
1) divides the technologies of two sections control polymerization temperatures, make polymerization time shorten to original 2/3.
2) first section reaction needs to carry out in the tank reactor of full-mixing type band scraper, makes to be aggregated under the low monomer equilibrium concentration to carry out, and avoided that reaction beginning Duan Yi blasts and the easy zone of gel wall built-up.Simultaneously not only make polymeric area secluding air (oxygen can hinder poly-) but also reaction zone is under the normal pressure, this is very favourable to volatile polymerization system is arranged.Second section need of polymerisation carry out in tower reactor (or multistage tank reactor), with guarantee polymerisation conversion reach 90% or more than.
3) nitrogen dioxide must be caught up with only to below 10/1000000ths with air in the nitric acid, adds excessive urea element (1-6 gram urea element/liter nitric acid) again and decomposes the accumulation that produces nitrogen dioxide to destroy nitric acid, because of the nitrogen dioxide accumulation can cause the polymerization system blast.
4) utilize cyan-hydrolysis to be amide groups.Draft the spinning technique of hydrolysis spinning solution.
Above-mentioned technology in April, 1978 through the Ministry of Chemical Industry tissue characterization, the paper of structure of reactor part can be read out in the reaction engineering annual meeting for the first time in chemical science in 1979, and is published on 25 pages of " Chemical Engineering " 1979 the 6th phases.The part achievement that homogeneous polymerization direct fabrics in the nitric acid (be called for short nitric acid one-step method) are made polyacrylonitrile fibre was published on 27 pages of " synthetic material " 1975 the 1st phases.The weak point of above-mentioned technology is that to make polyacrylonitrile fibril stability homogeneity lower, on 60 bundles and 100 bundle charing lines, fire carbon fiber only reach in by force level (intensity is more than or equal to 200Kg/mm
2, modulus is more than or equal to 18 tons/millimeter
2).
October nineteen eighty-two, the manufacturing technology by the high-strength 1 type polyacrylonitrile fibril for carbon fiber of the metallurgical office in Jilin chemical company-Shanghai City tissue characterization was improved on the basis of the above result.On hundred bundle charing lines, make the main performance of high-strength 1 type carbon fiber: intensity 250Kg/mm
2Its CV value is less than or equal to 10%, modulus 22T/mm
2Its CV value is less than or equal to 6%, and line density fluctuation CV value is less than or equal to 5.5%.But the homogeneity of product is still not enough, and 11.0 microns of the average diameters of precursor, the uneven rate of diameter be sometimes up to 13%, product percent of pass 80%.This improves being characterized as of technology: 1) strict control concentration of nitric acid is less than or equal to 1 ℃ in 67.1～67.15% scopes and polymerization temperature fluctuation, feed in raw material and stablize with the binomial crux index that guarantees polymerization for constant measures intermittent injecting, be that the polymer specific viscosity is that 0.80～0.86 its CV value is less than or equal to 5%, be preferably less than or equal 4%.Spinning fluid viscosity is that 200～300 pool (20 ℃) its CV values are less than or equal to 15%, is preferably less than or equals 10%.2) be less than or equal to for 3% control spinning head replacement cycle with end breakage rate, guaranteed that the fluctuation range of fiber number between each batch is less than or equal to ± 0.05 dawn.3) adopt acrylonitrile and methylene succinic acid binary copolymerization, the control section cyan-hydrolysis is an amide groups again, the scope of its degree of hydrolysis is 4～7%, and foregoing is write as " research of nitrate method polyacrylonitrile fibril for carbon fiber " paper and read out in the charcoal fiber symposium of nineteen eighty-three academy of sciences's hosting.
In order further to improve the intensity of carbon fiber, promptly bring up to the level of high-strength 2 types from the level of high-strength 1 type of prior art, improve the homogeneity of the qualification rate of product and carbon fiber and further investigate.The key here is to improve the homogeneity of polyacrylonitrile fibril for carbon fiber and the processing performance of charing.Particularly reduce the uneven rate of diameter and the fiber number stability bandwidth of precursor, it is mild and Thermogram stable to make when giving oxidation heat release, and the precursor that extension at break is also bigger when having high modulus is a purpose of the present invention.
The present invention adopts ternary polymerization to form to be acrylonitrile and a spot of methyl acrylate, methylene succinic acid (or acrylic acid etc.) copolymerization, wherein methyl acrylate (MA) accounts for total monomer amount (weight ratio) below 2%, preferably about 1%, methylene succinic acid accounts for total monomer amount (weight ratio) below 3%, and preferably 1.3～2.0%.The MA of introduction 1% just can obviously reduce the apparent viscosity (seeing Table 1) of spinning solution.
Table 1 is introduced methyl acrylate 1% back spinning fluid viscosity and is descended
Introduce methyl acrylate polymerization spinning solution and do not introduce methyl acrylate polymerization spinning solution
Specific viscosity concentration % viscosity specific viscosity concentration % viscosity
(pool) (pool)
0.81 14.5 209 0.80 14.7 240
It is nearly 17% that the spinning solution apparent viscosity descends, and the expanded ratio in its structural viscosity index and aperture also descends thereupon, so end breakage rate significantly reduces, spins to such an extent that the homogeneity of precursor improves.End breakage rate 3% obviously prolonged for the average replacement cycle of spinning head of index after introducing methyl acrylate in the table 2 as can be seen.
3% end breakage rate is the spinning head of index behind the table 2 introducing methyl acrylate
The average replacement cycle
The average replacement cycle of spinning head is formed in the days of operation copolymerization continuously
(hour)
27 acrylonitrile-methylene succinic acid binary 26
39 acrylonitrile-methylene succinic acid binary 29
21 acrylonitrile-methyl acrylate-methylene succinic acid ternary 68
But it is unfavorable to giving oxidation that the methyl acrylate addition surpasses above-mentioned scope, occurs the chemistry shortcoming on the ladder polymer structure that the cyano group cyclisation is generated.Carboxyl can bring out cyano-cyclization reaction strongly, but surpass above-mentioned scope the fiber heat resistance is excessively worsened, and is unfavorable for giving oxidation reaction on the contrary.
One of principal character of the present invention is that above-mentioned ternary polymerization of employing and control cyan-hydrolysis are amide groups, and the part hydrolysis of ester group is a carboxyl, thereby makes the precursor of polynary component, and its composition (percentage by weight) is:
Acrylonitrile 92.5
Methylene succinic acid 1～1.5
Methyl acrylate＜1
Acrylic acid＜1
Acrylamide 4～7
Polynary component precursor has been given play to following advantage: 1) differential thermal analysis (CDR-1 type instrument, 3.2 milligrams of sample-loading amounts, 10 ℃/minute of programming rates) result: 215～220 ℃ of initial exothermic temperatures, summit temperature (cyclisation temperature) T
p=284～286 ℃, T=3 ℃ of reaction peak height △, the effect that promptly shows tangible mitigation cyano-cyclization reaction exothermic peak can reduce the cracking and the chain rupture of macromolecular chain when giving oxidation, helps producing high strong type carbon fiber.2) amide groups when heating easily and the carboxyl interlinkage on the macromolecular chain, make Stability Analysis of Structures, reduce chain rupture destruction when giving oxidation.3) hydrophilic radical increases, and set value becomes big when wet-formed, very helps making the less coagulated yarn of shortcoming of homogeneous.4) structural viscosity index of polynary component copolymer nitric acid spinning solution descends, and helps reducing when wet-formed end breakage rate.5) hot drawdown improves, and the homogeneity of precursor is improved.6) giving oxidization time can obviously foreshorten to and be less than or equal to 45 fens.
After concentration of nitric acid (67～68%) was determined, degree of hydrolysis depended on the temperature and the time of staying of spinning solution.Our research is learnt at polymer concentration lower, and the initial hydrolysis of polymer is to belong to zero-order reaction, and it is linear equation that actual measurement obtains under all temps that degree of hydrolysis returns with time of staying relation:
h＝Kt+A
H is the acrylonitrile unit mole percent (degree of hydrolysis %) of hydrolysis
T be the time of staying (hour)
K, A constant
In 0～20 ℃ of scope of temperature, try to achieve K=0.02～0.32
Cyan-hydrolysis activation energy=23.1 kilocalorie/gram molecule
Keep certain time of staying of certain polymerization temperature and corresponding selection in control hydrolysis degree fluctuation at 3-6%(with mole), be in 4～7% scopes by weight.
The detection of degree of hydrolysis fluctuation, we get 2250 centimetres of itrile group with infrared spectrogram
-1Bands of a spectrum and C=0 1680 centimetres
-1The optical density ratio of bands of a spectrum
R＝ (D1680)/(D2250)
For detecting index, try to achieve the unit mole percent (degree of hydrolysis %) of acrylonitrile hydrolysis.Also need to use again the test of DTA spectrogram, require summit temperature T
p(cyclisation temperature) fluctuation must be less than or equal to ± 2 ℃.
The variation of morphosis rearrangement and order also takes place in precursor except chemical change takes place in giving heat of oxidation stabilization process.Precursor faces and applies suitable tension force when cyclization takes place and the fiber order is changed decisive influence is arranged giving oxidation.The present invention tries hard to make the X-ray degree of orientation 80～82% in spinning, the also bigger precursor of extension at break under the higher prerequisite of modulus.To guarantee that precursor has good performance of technical process when oxidation applies than hightension giving, and makes the intensity height and the homogeneity that make carbon fiber good.If the drawing-off of excessive reinforcement precursor and tension force typing can make the high X-light degree of orientation (86%) and high density, the precursor of low extension at break, charing carbon fiber strength as a result disperses greatly, on the contrary effect is not good.Precursor modulus index request is high wishes it is greatly conflicting with extension at break.Improve modulus and can reduce extension at break.Another feature of the present invention is can make modulus on spinning and the aftertreatment technology about 70 gram/dawn, extension at break 17%, and its fluctuation range of the strict control of energy is 17 ± 2% precursor, the present invention adopts that to give 8～10% boiling water after 8.5～9.5 times of the hot water drawing-offs lax, be equal to or less than 100 ℃ of following drying under tensions then, be warming up to the technology of 120～140 ℃ of nervous typings again.The hot water drawing-off divided for two steps, gave earlier 1.5～2.0 times of drawing-offs in 85～90 ℃ of hot water, and to reduce the swelling capacity of tow, once being drawing to general times then in boiling water is 8.5～9.5 times.The precursor average diameter is brought up to 11.5 microns controls by existing 11.0 microns.Guarantee the negative drawing-off 15～30% of spinning head, preferably be not less than 20%.The end breakage rate and the uneven rate of diameter of precursor are obviously descended.
The advantage that the present invention compared with prior art has:
1) homogeneity and the charring process performance that makes precursor is significantly improved, and sees the following form:
284 ℃ of the summit temperatures of the DTA of precursor, fluctuation be less than or equal to ± and 2 ℃, △ T is less than or equal to 3 ℃, and the modulus of precursor is about 70 gram/dawn, extension at break 17 ± 2%.
The uneven rate of the diameter of precursor drops to from 13% and is less than or equal to 7%.
2) the present invention makes precursor, and the required oxidization time that gives can foreshorten to and is less than or equal to 45 fens when adopting the air oxidation process charing.Obtain the 250Kg/mm of carbon fiber strength from prior art
2Bring up to 300Kg/mm
2Or more than.With more than or equal to 250Kg/mm
2, 22 tons/mm of modulus
2For basic calculation carbon fiber qualification rate from 80% of prior art bring up to 95% or more than.The coefficient of variation of line density is less than or equal to 3%.
Example
Ternary polymerization is formed: acrylonitrile: methyl acrylate: methylene succinic acid=97.7: 1.0: 1.3(Wt%).610 gram/times of total monomer inlet amount.Polymerization initiator is an ammonium persulfate, acetylacetone,2,4-pentanedione, and ferric nitrate is 1.3～1.8 to amount of monomer Wt% respectively; 0.2～0.5; 0.05～0.2.Concentration of nitric acid 67～68% And give earlier nitrogen oxide to the content that blows down wherein with nitrogen and add the plain 2 grams per liter nitric acid of urea after less than 10PPm.Monomer accounts for whole material gross weights (concentration feeds intake) 15.5%.Calculate the feeding quantity of various materials in above-mentioned each ratio.
Polymerization is to carry out on tank reactor and continuous polymerization unit that tower reactor is connected.Divide two sections and carry out temperature control, 9 ± 1 ℃ of still reaction actuator temperatures, 15 ± 1 ℃ of tower reactor temperature, polymerization total residence time 18 hours, polymerisation conversion is greater than 90%.Polymer specific viscosity 0.82～0.85 obtains the spinning solution that viscosity 200～300 is moored, and filters through filter, sends into the deaeration still.Deaeration still vacuum overbottom pressure 20～25mmHg post, 17～18 ℃ of temperature, spinning solution after the deaeration is sent to spinning.
Spinning line is: solidify-sour water washes-give drawing-off-boiling water drawing-off-boiling water and relax-once oil-drying-secondary oils-finalizes the design-roll up and scratch into tube
Spinning head is 1000 holes * φ 0.07mm, and the hole draw ratio is 2: 1, and precision 0.002, material are tantalum.Coagulating bath 36% aqueous solution of nitric acid, 0 ± 1 ℃ of temperature, spinning head is born drawing-off 20%.Sour water is washed and is room temperature, PH＞5 on the tow of washing back.Giving the drawing-off bath is 85～90 ℃ of hot water, 1.5～2.0 times of drafting multiples.Two sections total draft multiples are 8.5～9.0 times after the boiling water drawing-off, boiling water 8～10%, the 100 ℃ of drying under tensions that relax, and 140 ℃ of nervous typings, volume is scratched 40.5 meters/minute of speed.
Spin the main performance index of precursor:
The fiber number 1.1(dawn), its CV%≤3.5, the uneven rate of diameter is less than or equal to 7%.Wherein diameter is less than the radical of 7u: less than 4/100 rhizoid samples, diameter is greater than the radical of 12u: less than 4/100 rhizoid samples, about average diameter 11.5u.Intensity is more than or equal to 4.6 gram/dawn; Its CV% is less than or equal to 6.Extension at break 17 ± 2%; 70 ± 10 gram/dawn of modulus.Radical/bundle is more than or equal to 970.
Adopt the air oxidation process charing, give 200～300 ℃ of oxidizing temperatures, stretch 10～15%, give 45 minutes oxidation time of staying.Intensification is from 300～1000 ℃, 1200～1300 ℃ in high temperature carbonization stove, protective gas: high-purity N
2(purity 99.995%).Carbonization time 7 seconds is kept certain malleation in the retort.
Obtain charcoal fiber main performance and index:
Intensity 330Kg/mm
2, its CV% is less than or equal to 5.Modulus 21～22T/mm
2Extension at break 1.5～1.6%.About line density 0.057 gram/rice, its CV% is less than or equal to 3.
Claims (3)
1, the present invention is a kind of technology of making carbon fiber with polynary component polyacrylonitrile fibril.Adopt the polymerizating body equipment of full-mixing type (the band scraper) tank reactor and tower (or multistage kettle formula) reactor polyphone, acrylonitrile, methylene succinic acid, methyl acrylate ternary component, the chelate of ammonium persulfate-ferric acetyl acetonade (or acetylacetone copper) is that polymerization initiator divides two sections temperature controls to carry out homogeneous polymerization in aqueous solution of nitric acid, obtains spinning solution makes polynary component through wet spinning precursor.Solvent nitric acid must add stabilizing agent (as the urea element) and destroy the accumulation of nitrogen oxide to guarantee polymerization system safety.The weight percent that the invention is characterized in three kinds of monomers is:
Acrylonitrile is 97.5 more than or equal to 95 the bests
It is 1.0 that methyl acrylate is less than or equal to 2 the bests
It is 1.3～2.0 that methylene succinic acid is less than or equal to 3 the bests
And be zero-order reaction according to the hydrolysis of acrylonitrile in 67～68% aqueous solution of nitric acid, adjust reaction temperature and time of staying control hydrolysis degree and be 3～6% (in moles) and make and contain the polyacrylonitrile fibril that acrylonitrile, methylene succinic acid, methyl acrylate, acrylic acid and acrylamide five-tuple become.
2, as the said technology of claim 1, it is characterized in that 1.5～2.0 times of the drawing-offs in 85～90 ℃ hot water earlier of the precursor that just spins, again after boiling water is drawing to 8.5～9.5 times of general times, again through boiling water lax 8～10%, enter drying under tension in the baking oven that is equal to or less than 100 ℃, be warming up to again 120～140 ℃ of nervous typings and the high-strength carbon fiber polyacrylonitrile fibril.
3, the prepared carbon fiber of the present invention is characterized in that with many components polyacrylonitrile fibril:
Chemical composition (by weight percentage)
Acrylonitrile 92 ± 0.5
Methylene succinic acid is less than or equal to 1.5
Methyl acrylate＜1
Acrylic acid＜1
Acrylamide 4～7
The key technical indexes:
The fiber number 1.1(dawn)
The uneven rate of diameter is less than or equal to 7%
Diameter greater than 12 microns radical less than 4/100 rhizoids
Diameter less than 7 microns radical less than 4/100 rhizoids
Modulus 70 ± 10(gram/dawn)
Extension at break 17 ± 2%
End breakage rate is less than or equal to 3%
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85103318 CN1007740B (en) | 1985-04-30 | 1985-04-30 | Multi-component polyacrylonitrile raw filment for carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85103318 CN1007740B (en) | 1985-04-30 | 1985-04-30 | Multi-component polyacrylonitrile raw filment for carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85103318A true CN85103318A (en) | 1987-04-08 |
| CN1007740B CN1007740B (en) | 1990-04-25 |
Family
ID=4793106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85103318 Expired CN1007740B (en) | 1985-04-30 | 1985-04-30 | Multi-component polyacrylonitrile raw filment for carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1007740B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105793C (en) * | 1997-08-27 | 2003-04-16 | 三菱丽阳株式会社 | Acrylonitrile-based precursor fiber for carbon fiber, process for producing the same, and carbon fiber obtained from the precursor fiber |
| CN101724922B (en) * | 2009-11-26 | 2012-09-05 | 中复神鹰碳纤维有限责任公司 | Method for preparing high-strength polyacrylonitrile-based precursor for carbon fiber |
| CN107208324A (en) * | 2014-12-29 | 2017-09-26 | 塞特工业公司 | The densification of polyacrylonitrile fibre |
| CN110093677A (en) * | 2019-05-20 | 2019-08-06 | 中国科学院山西煤炭化学研究所 | A kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre and preparation method thereof |
| CN114457436A (en) * | 2020-11-10 | 2022-05-10 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber precursor, tows and application method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768791B (en) * | 2010-02-10 | 2011-11-09 | 北京化工大学 | Polyacrylonitrile-based hollow carbon fiber precursor preparation method |
-
1985
- 1985-04-30 CN CN 85103318 patent/CN1007740B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105793C (en) * | 1997-08-27 | 2003-04-16 | 三菱丽阳株式会社 | Acrylonitrile-based precursor fiber for carbon fiber, process for producing the same, and carbon fiber obtained from the precursor fiber |
| CN101724922B (en) * | 2009-11-26 | 2012-09-05 | 中复神鹰碳纤维有限责任公司 | Method for preparing high-strength polyacrylonitrile-based precursor for carbon fiber |
| CN107208324A (en) * | 2014-12-29 | 2017-09-26 | 塞特工业公司 | The densification of polyacrylonitrile fibre |
| CN110093677A (en) * | 2019-05-20 | 2019-08-06 | 中国科学院山西煤炭化学研究所 | A kind of polyacrylonitrile fibre, polyacrylonitrile-based carbon fibre and preparation method thereof |
| CN110093677B (en) * | 2019-05-20 | 2021-08-31 | 中国科学院山西煤炭化学研究所 | A kind of polyacrylonitrile fiber, polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN114457436A (en) * | 2020-11-10 | 2022-05-10 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber precursor, tows and application method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1007740B (en) | 1990-04-25 |
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