CN103710792A - Preparation method of polyacrylonitrile-based carbon fiber - Google Patents
Preparation method of polyacrylonitrile-based carbon fiber Download PDFInfo
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- CN103710792A CN103710792A CN201210377101.1A CN201210377101A CN103710792A CN 103710792 A CN103710792 A CN 103710792A CN 201210377101 A CN201210377101 A CN 201210377101A CN 103710792 A CN103710792 A CN 103710792A
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- Prior art keywords
- polyacrylonitrile
- solvent
- based carbon
- preparation
- carbon fibre
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920000049 Carbon (fiber) Polymers 0.000 title abstract description 11
- 239000004917 carbon fiber Substances 0.000 title abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000000835 fiber Substances 0.000 claims abstract description 30
- 238000009987 spinning Methods 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 9
- 230000001112 coagulating effect Effects 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 9
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 5
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract 1
- 229940113088 dimethylacetamide Drugs 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 238000005086 pumping Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 stretch Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
Landscapes
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a preparation method of polyacrylonitrile-based carbon fiber, which solves the problems of high equipment investment and large public engineering consumption in prior art. The method comprises the following steps: a)polyacrylonitrile powder is dissolved by a solvent I to slurry under the operation temperature T1 at 15-95 DEG C; b)a solvent II and the slurry are contacted to prepare a spinning raw liquid under the operation temperature T2 at 30-99 DEG C; c)the spinning raw liquid and dimethyl acetamide are mixed in a spinning machine, and can be shaped in the spinning machine through a coagulating bath spinning duct to obtain nascent fiber; and d)the nascent fiber is washed, stretched, oiled, dried and then is performed with oxidation and carbonization treatment to obtain the polyacrylonitrile-based carbon fiber. The preparation method better solves the problems, and can be used in the industrial production for producing polyacrylonitrile-based carbon fiber.
Description
Technical field
The present invention relates to a kind of preparation method of polyacrylonitrile-based carbon fibre.
Background technology
Polyacrylonitrile-radical (PAN) carbon fiber is the new material growing up the sixties in 20th century, because of excellent properties such as it has that quality is light, specific strength is high, specific modulus is high, high temperature resistant, corrosion-resistant, wear-resisting, antifatigue, conduction, heat conduction, be widely used in the military industries such as satellite, carrier rocket, tactical missile, spaceship, become indispensable material in space flight and aviation industry.
Document CN200710056346.3 discloses a kind of preparation method of polyacrylonitrile base carbon fiber precursors, polyacrylonitrile base carbon fiber precursors is prepared in the aqueous-phase suspending copolymerization that ammonium persulfate-ammonium sulfite or ammonium bisulfite be initiator system of take, with polymer, it is raw material, at-18～0 ℃, make 16～20Wt% slurry, and be evacuated to 40～95Kpa, in the time of 40～55 ℃, dissolve 1～2 hour: then, 70～80 ℃ of spinning solutions are extruded to moulding in the spin duct entering in coagulating bath through spinning head, through the negative drawing-off of coagulating bath, acquisition PAN as-spun fibre; Through hot water wash, remove solvent; Stretch simultaneously, oil, compacting by drying, oven dry drawing-off, obtain PAN based precursor.The method in preparing spinning solution process, adopt-18～0 ℃ compared with low operating temperature, special refrigerator need to be set cold is provided, the problem that have that equipment investment is high, public work consumption is many.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists the problem that equipment investment is high, public work consumption is many, and a kind of preparation method of new polyacrylonitrile-based carbon fibre is provided.It is low that the method has equipment investment, the feature that public work consumption is few.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of polyacrylonitrile-based carbon fibre, comprises the following steps:
A) by polyacrylonitrile powder, in operating temperature, be T
1under=15 ~ 95 ℃ of conditions, by solvent I, dissolve and make slurry; Wherein, solvent I is selected from least one in potassium rhodanide, sodium sulfocyanate, sodium thiosulfate, sodium chlorate or sodium sulphate, and the weight ratio of solvent I and polyacrylonitrile powder is (1 ~ 5): 1;
B) in operating temperature, be T
2under=30 ~ 99 ℃ of conditions, solvent II is contacted with slurry, make spinning solution; Wherein, solvent II is selected from least one in potassium rhodanide, sodium sulfocyanate, sodium thiosulfate, sodium chlorate or sodium sulphate, and the weight ratio of solvent II and slurry is (1 ~ 5): 1;
C) described spinning solution is mixed in spinning machine with dimethylacetylamide, and in spinning machine by the moulding of coagulating bath spin duct, obtain as-spun fibre;
D) described as-spun fibre is through washing, stretch, oil, be dried, drying, then through oxidation, carbonization treatment, obtains described polyacrylonitrile-based carbon fibre.
In technique scheme, the weight percent concentration of solvent I is 10 ~ 45%, and the weight percent concentration of solvent II is 35 ~ 75%.Preferred version is that solvent I and solvent II are identical compounds.T
1preferable range is 20 ~ 90 ℃, and more preferably scope is 25 ~ 85 ℃, and most preferred range is 30 ~ 70 ℃.T
2preferable range is 35 ~ 95 ℃, and more preferably scope is 40 ~ 90 ℃, and most preferred range is 60 ~ 80 ℃.The weight ratio preferable range of solvent I and polyacrylonitrile powder is (1 ~ 4): 1, and the weight ratio preferable range of solvent II and slurry is (1 ~ 4): 1.The inventive method preferred version is T
2>=T
1, more preferably scheme is (T
2-T
1)>=10 ~ 30 ℃.In step c), the weight ratio of spinning solution and dimethylacetylamide is 40 ~ 70%, and the temperature of coagulating bath is 30 ~ 60 ℃.The molecular weight preferable range of polyacrylonitrile powder is 8 ~ 100,000.
In the inventive method, the washing of as-spun fibre, stretch, oil, be dried, oven dry, oxidation, carbonization treatment process be known in the art.For example, can be first with the hot wash of 80 ~ 90 ℃ 6 times, and stretch 2 ~ 4 times, then through the hot wash of 91 ~ 100 ℃ 4 times, stretch 2 ~ 3 times, then through oiling, 150 ~ 180 ℃ dry, dry, finally under ℃ condition of heating furnace ~ 1200, be oxidized, carbonization treatment.
The cyano group that polyacrylonitrile particles contains strong polarity, so polymer molecular chain has the trend being arranged in parallel, and forms crystalline texture, and dissolubility is reduced.In the inventive method, first polyacrylonitrile and solvent I (one of 5 kinds of solution such as potassium rhodanide, sodium sulfocyanate, sodium thiosulfate, sodium chlorate, sodium sulphate) are first carried out low temperature dispersion, make slurry, make solvent I be diffused into each particle of condensate around.Then, polymer dispersed slurry enters dissolving base together with solvent II under higher temperature, and high temperature makes K
+or Na
+ion enters rapidly polymeric crystal structure, with CN
-base combination, has destroyed the connection between polymer molecule and has dissolved, and forms spinning solution; Spinning solution obtains the polyacrylonitrile-based carbon fibre of tow 12K again through a series of processing.Adopt the inventive method, compared with prior art, do not need freezing equipment, also do not need vaccum-pumping equipment, there is the low feature of equipment investment.In addition, owing to not needing refrigerator that cold is provided, do not need vaccum-pumping equipment yet, and heat required heat, can make full use of the unnecessary exhaust steam in chemical plant or spent hot water, so can make power consumption reduce by 70%.The polyacrylonitrile-based carbon fibre that the inventive method makes, carbon fiber line density is 800mg/m, tensile strength >=3.5Gpa, tensile modulus >=225 Gpa, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1]
Molecular weight is that 100,000 polyacrylonitrile material and concentration are that 20% potassium rhodanide material (solvent I) is at T
1under=30 ℃ of conditions, mix, be deployed into slurry; The weight ratio of potassium rhodanide material and polyacrylonitrile material is 3:1.Then, slurry is at T
2under=70 ℃ of conditions, be 60% potassium rhodanide material (solvent II) mixed dissolution with concentration; The weight ratio of potassium rhodanide material and slurry is 2:1.Finally, after press filtration, filtration, obtain spinning solution.
Spinning solution and dimethylacetylamide (weight ratio is 50%) be mixed being incorporated in spinning machine by coagulating bath (temperature is 40 ℃) spin duct moulding in spinning machine, acquisition PAN as-spun fibre.This PAN hot wash for as-spun fibre, stretch, oil, be dried, dry and obtain clean PAN as-spun fibre, then by the PAN base carbon fibre that heating furnace is oxidized, carbonization treatment obtains tow 12K.This carbon fiber line density is 800mg/m, tensile strength >=3.5 Gpa, tensile modulus >=225 Gpa.
Whole process does not need refrigerator that cold is provided, and does not need vaccum-pumping equipment yet, and heat required heat, is the exhaust steam that utilizes chemical plant unnecessary, and power consumption reduces by 70.2%.
[embodiment 2]
With [embodiment 1], just solvent I and solvent II are hypo solution, and the concentration of solvent I is 25%, and the concentration of solvent II is 50%.
Whole process does not need refrigerator that cold is provided, and does not need vaccum-pumping equipment yet, and heat required heat, is the exhaust steam that utilizes chemical plant unnecessary, and power consumption reduces by 71.8%.The carbon fiber line density making is 800mg/m, tensile strength >=3.5 Gpa, tensile modulus >=225 Gpa.
[embodiment 3]
With [embodiment 2], be T
1=35 ℃, T
2=75 ℃.
Whole process does not need refrigerator that cold is provided, and does not need vaccum-pumping equipment yet, and heat required heat, is the exhaust steam that utilizes chemical plant unnecessary, and power consumption reduces by 70.9%.The carbon fiber line density making is 800mg/m, tensile strength >=3.5 Gpa, tensile modulus >=225 Gpa.
Claims (10)
1. a preparation method for polyacrylonitrile-based carbon fibre, comprises the following steps:
A) by polyacrylonitrile powder, in operating temperature, be T
1under=15 ~ 95 ℃ of conditions, by solvent I, dissolve and make slurry; Wherein, solvent I is selected from least one in potassium rhodanide, sodium sulfocyanate, sodium thiosulfate, sodium chlorate or sodium sulphate, and the weight ratio of solvent I and polyacrylonitrile powder is (1 ~ 5): 1;
B) in operating temperature, be T
2under=30 ~ 99 ℃ of conditions, solvent II is contacted with slurry, make spinning solution; Wherein, solvent II is selected from least one in potassium rhodanide, sodium sulfocyanate, sodium thiosulfate, sodium chlorate or sodium sulphate, and the weight ratio of solvent II and slurry is (1 ~ 5): 1;
C) described spinning solution is mixed in spinning machine with dimethylacetylamide, and in spinning machine by the moulding of coagulating bath spin duct, obtain as-spun fibre;
D) described as-spun fibre is through washing, stretch, oil, be dried, drying, then through oxidation, carbonization treatment, obtains described polyacrylonitrile-based carbon fibre.
2. the preparation method of polyacrylonitrile-based carbon fibre according to claim 1, the weight concentration percentage that it is characterized in that solvent I is 10 ~ 45%, and the weight percent concentration of solvent II is 35 ~ 75%, and solvent I and solvent II are identical compounds.
3. the preparation method of polyacrylonitrile-based carbon fibre according to claim 1, the weight ratio that it is characterized in that solvent I and polyacrylonitrile powder is (1 ~ 4): 1, the weight ratio of solvent II and slurry is (1 ~ 4): 1.
4. the preparation method of polyacrylonitrile-based carbon fibre according to claim 1, is characterized in that T
1=20 ~ 90 ℃, T
2=35 ~ 95 ℃.
5. the preparation method of polyacrylonitrile-based carbon fibre according to claim 4, is characterized in that T
1=25 ~ 85 ℃, T
2=40 ~ 90 ℃.
6. the preparation method of polyacrylonitrile-based carbon fibre stoste according to claim 5, is characterized in that T
1=30 ~ 70 ℃, T
2=60 ~ 80 ℃.
7. the preparation method of polyacrylonitrile-based carbon fibre according to claim 1, is characterized in that T
2>=T
1.
8. the preparation method of polyacrylonitrile-based carbon fibre according to claim 7, is characterized in that (T
2-T
1)>=10 ~ 30 ℃.
9. the preparation method of polyacrylonitrile-based carbon fibre according to claim 1, is characterized in that in step c), and the weight ratio of spinning solution and dimethylacetylamide is 40 ~ 70%, and the temperature of coagulating bath is 30 ~ 60 ℃.
10. the preparation method of polyacrylonitrile-based carbon fibre according to claim 1, the molecular weight that it is characterized in that polyacrylonitrile powder is 8 ~ 100,000.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210377101.1A CN103710792A (en) | 2012-10-08 | 2012-10-08 | Preparation method of polyacrylonitrile-based carbon fiber |
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| CN201210377101.1A CN103710792A (en) | 2012-10-08 | 2012-10-08 | Preparation method of polyacrylonitrile-based carbon fiber |
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| CN103710792A true CN103710792A (en) | 2014-04-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952797A (en) * | 2014-04-23 | 2014-07-30 | 北京化工大学 | Preparation method of wet-process high-strength polyacrylonitrile-based carbon fiber |
| CN109312497A (en) * | 2016-06-30 | 2019-02-05 | 东丽株式会社 | Carbon fiber bundle and its manufacturing method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2010100970A (en) * | 2008-10-24 | 2010-05-06 | Toray Ind Inc | Method for producing carbon fiber |
| CN102277644A (en) * | 2011-06-30 | 2011-12-14 | 东华大学 | Polyacrylonitrile-based protofilaments modified by phenolic resin and preparation method thereof |
| CN102400234A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber precursor spinning solution |
-
2012
- 2012-10-08 CN CN201210377101.1A patent/CN103710792A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2010100970A (en) * | 2008-10-24 | 2010-05-06 | Toray Ind Inc | Method for producing carbon fiber |
| CN102400234A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber precursor spinning solution |
| CN102277644A (en) * | 2011-06-30 | 2011-12-14 | 东华大学 | Polyacrylonitrile-based protofilaments modified by phenolic resin and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952797A (en) * | 2014-04-23 | 2014-07-30 | 北京化工大学 | Preparation method of wet-process high-strength polyacrylonitrile-based carbon fiber |
| CN109312497A (en) * | 2016-06-30 | 2019-02-05 | 东丽株式会社 | Carbon fiber bundle and its manufacturing method |
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