CN1587457A - Process for preparing precursor fiber of cellulose base carbon fiber - Google Patents
Process for preparing precursor fiber of cellulose base carbon fiber Download PDFInfo
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- CN1587457A CN1587457A CN 200410052885 CN200410052885A CN1587457A CN 1587457 A CN1587457 A CN 1587457A CN 200410052885 CN200410052885 CN 200410052885 CN 200410052885 A CN200410052885 A CN 200410052885A CN 1587457 A CN1587457 A CN 1587457A
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Abstract
The present invention relates to preparation process of precursor fiber of cellulose base carbon fiber in chemical fiber production. The preparation process includes mixing concentrated NMMO aqua and carbon black for carbon black water in the weight ratio of 20-10000, decomprssion distillation to obtain NMMO/carbon black solution with water content 24-28 wt%, adding the mixtue of sliced cellulose pulp and NMMO/carbon black solution in the weight ratio of 5-15 to 100 into dissolving reactor, swelling and stirring at 70-90 deg.c, raising the temperature to 90-120 deg.c, stirring and decomprssion distillation to eliminate water and form cellulose/NMMO/carbon black spinning liquid with water content of 12-14 wt%, and dry-wet spinning to obtain the precursor fiber. The present invention has high carbonizing yield, high mechanical performance of the carbon fiber, raised spinnability of the spinning liquid, non-toxic solvent, high solvent recovering rate and environment friendship.
Description
Technical field
The present invention relates to the preparation method of the precursor fiber of carbon fiber in the chemical fibre industry, be meant especially and in N-methylmorpholine oxide (NMMO) aqueous solution, add the technology that carbon black comes the precursor fiber of the plain base carbon fibre of spinning fibre.Utilize the prepared carbon fiber of this precursor fiber to have performances such as high-strength, Gao Mo, anti-ablation, can be widely used in fields such as Aeronautics and Astronautics, military affairs, the energy, traffic and medical science.
Background technology
Carbon fiber is fibrous material with carbon element, and its preparation generally is to use the organic polymer fiber as precursor fiber, obtains through peroxidating and carbonization treatment.Three larger precursor fibers of preparation carbon fiber are polyacrylonitrile (PAN) fiber, pitch fibers and cellulose fibre at present.On carbon fiber market, the world, PAN base carbon fibre and asphalt base carbon fiber, be all to be to be in the absolute predominance status on the combination property or on volume of production and marketing, so PAN and the pitch precursor fiber that is used for carbon fiber carried out a large amount of scientific researches and formed many patents.Wherein relate to carbon fiber and US6641915, JP2003020516, US6428891, RU2122607, US6326451 etc. are arranged with the patent of PAN precursor fiber manufacture method; Relate to carbon fiber and US5057341, CA1223225, US4578177, JP60133087, US4402928 etc. are arranged with the patent of pitch precursor fibre manufacture.
The cellulose base carbon fiber is because the carbonization yield is low, cost is high, intensity is not as good as polyacrylonitrile-radical and asphalt base carbon fiber, and its Application Areas has been subjected to certain restriction, only accounts for ratio (about 1～2%) seldom at present in world's carbon fiber production.Therefore, also less relatively to the research of the precursor fiber of cellulose base carbon fiber, almost there is not relevant patent.But because purity height, the biocompatibility of cellulose base carbon fiber are good and ablation resistance good, thereby other irreplaceable status of two based carbon fibers are arranged in fields such as Aeronautics and Astronautics, military affairs and medical science.At present, the precursor fiber that is used for the cellulose base carbon fiber mainly is the viscose glue strong fiber, but traditional viscose is shortcomings such as fabiform, degree of crystallinity and the degree of orientation are all lower, short texture because of skin-core structure, cross section are arranged, be difficult to prepare the carbon fiber of high-quality, and also there are shortcomings such as process route is long, energy consumption is big, environmental pollution is serious in the production of viscose.
In recent years, reported the precursor fiber of employing Lyocell fiber on Wu Qilin of Donghua University (Q.Wu) and the Peng Shunjin periodicals abroad such as (S.Peng) as carbon fiber.The Lyocell fiber is a kind of novel cellulose fibre, and it is cellulose pulp directly to be dissolved in N-methylmorpholine oxide (NMMO) aqueous solution form cellulose solution, makes by dry-wet spinning then.Simple, the cleaning of Lyocell production technology, compare with traditional viscose, the Lyocell fiber has characteristics such as round section morphology, even structure, the degree of orientation and degree of crystallinity height, mechanical property be good, and, its fiber number can be controlled by adjusting spinning technology parameter, can prepare performance than the better cellulose base carbon fiber of traditional viscose-based carbon fiber with this fiber as precursor fiber, but this method still exists the problems such as cost is bigger that make because of the carbonization yield is not high enough.Therefore, when reducing environmental pollution, further improve the carbonization yield of cellulose base carbon fiber, and improve its mechanical property, become one of focus of scientist's concern, but still do not have relevant patent up to now.
Summary of the invention
The purpose of this invention is to provide that a kind of carbonization yield height, cost are low, the mechanical property preparation method of the precursor fiber of high-quality cellulose base carbon fiber preferably.
For addressing this problem, adopt following technical scheme:
1. be 400～1000 cellulose cotton pulp or wood pulp with the degree of polymerization, be cut to the small pieces of 0.5～4cm * 0.5～4cm with the pulp shredding machine, then with these small pieces in vacuum-9 * 10
4～-5 * 10
4Pa and 30～50 ℃ of following desiccated balances 6～12 hours make its moisture content reach 2～4%;
With N-methylmorpholine oxide (NMMO) aqueous solution inspissation under reduced pressure, making its moisture is 20～30%;
Purchase solid content and be 0.1～1%, the sooty water dispersion liquid of particle diameter 10nm～2 μ m is as additive.
With contained carbon black in N-methylmorpholine oxide (NMMO) aqueous solution of resulting inspissation in above-mentioned 1 and the sooty water dispersion liquid with 20～10000: 1 weight ratio preparation, after mixing 2～4 hours, decompression distillation to moisture is 24～28% NMMO/ carbon black solution again.
With in above-mentioned 1 in the cellulose pulp small pieces and above-mentioned 2 of desiccated balance resulting NMMO/ carbon black solution with 5～15: 100 weight ratio joins in the dissolution kettle, after stirring through the brute force of the quiet swelling of 20～40min, 20～60min under 70～90 ℃, be warming up to 90～120 ℃ again, remove moisture through stirring, decompression distillation, generate moisture and be cellulose/NMMO/ carbon black solution of 12%～14%, promptly obtain the spinning solution of precursor fiber of the cellulose base carbon fiber of black.
4. the temperature with above-mentioned 3 resulting spinning solutions is adjusted to 85～100 ℃, through the spinnerets ejection, behind the air gap (being the air layer between spinning plate surface and the coagulating bath face) by 5～300mm, enter solidification forming in the NMMO aqueous solution of pure water or low concentration (＜20%), after washing, be wound into tube, obtain containing the precursor fiber of the cellulose base carbon fiber of 0.05%～52% carbon black after the drying.
Advantage of the present invention is as additive with the sooty water dispersion liquid, come the precursor fiber of the plain base carbon fibre of spinning fibre, experimental result proves: added the precursor fiber Heat stability is good of carbon black, anti-ablation, the carbonization yield for preparing carbon fiber under the same conditions is significantly increased, thereby has solved the low difficult point of carbonization yield of cellulose base carbon fiber first; By adding carbon black, can make the structure of precursor fiber fine and close more, the carbon fiber that makes thus is also dense, makes the corresponding raising with modulus of intensity of carbon fiber; It is less even reach nano level sooty water dispersion liquid as additive that use contains particle diameter, can be evenly dispersed in the NMMO aqueous solution, can be made into the cellulose spin dope of good spinnability on this basis; The NMMO solvent that uses has nontoxic and the high characteristics such as (99.7%) of the rate of recovery, and spinning technique is simple, environmentally safe.
The specific embodiment:
Embodiment 1: with the degree of polymerization is 500 cellulose cotton pulp, is cut to the small pieces of 2cm * 2cm with the pulp shredding machine, with these small pieces in vacuum-9 * 10
4Pa and 50 ℃ of following desiccated balances made its moisture content reach 2% in 6 hours; With 2800 gram moisture is that 50% the NMMO aqueous solution distills under reduced pressure, obtains 1885 gram moisture and be 26% the NMMO aqueous solution; Additive is the nano carbon black aqueous dispersions of solid content 0.4%, particle diameter 10nm.
With the 1885 gram moisture that obtain is that 26% the NMMO aqueous solution mixes on magnetic stirring apparatus with 4000 gram sooty water dispersion liquids and stirred 3 hours, and decompression distillation goes out 3984 gram water then, and it is 25.8% NMMO/ sooty water solution that formation 1901 restrains moisture.
Above-mentioned NMMO/ sooty water solution and the 160 cellulose cotton pulp small pieces crossed of gram dried are placed dissolution kettle, after the brute force of 80 ℃ of following quiet swellings through 30min, 30min stirs, be warming up to 90 ℃ again, through stir, decompression distillation removes moisture, generates moisture and be the spinning solution of the cellulose base carbon fiber precursor fiber of 13.3% black.
After then resulting spinning solution being adjusted to 92～93 ℃, spinneret orifice ejection through 100 holes, aperture 0.08mm, by length is the air gap layer of 5cm, enter solidification forming in the pure water, after washing, be wound into tube, obtaining after the drying doing is by force the precursor fiber of the cellulose base carbon fiber that contains 9.1% carbon black of 4.5cN/dtex, carbonization yield with this precursor fiber production carbon fiber can improve about 6%, and the carbon fiber that carbon fiber strength for preparing after oxidation, carbonization treatment and modular ratio are not added the carbon black preparation improves 40% and 55% respectively.
Claims (2)
1. the preparation method of the precursor fiber of cellulose base carbon fiber is characterized in that:
A) with the degree of polymerization be 400～1000 cellulose cotton pulp or wood pulp, be cut to the small pieces of 0.5～4cm * 0.5～4cm with the pulp shredding machine, then with these small pieces in vacuum-9 * 10
4～-5 * 10
4Pa and 30～50 ℃ of following desiccated balances 6～12 hours make its moisture content reach 2～4%;
B) with N-methylmorpholine oxide water solution inspissation under reduced pressure, making its moisture is 20～30%;
C) purchase that solid content is 0.1～1%, the sooty water dispersion liquid of particle diameter 10nm～2 μ m;
D) with aforementioned B) the N-methylmorpholine oxide water solution and the C of the inspissation of gained) in the described sooty water dispersion liquid contained carbon black with 20～10000: 1 weight ratio preparation, after mixing 2～4 hours, decompression distillation to moisture is N-methylmorpholine oxide/carbon black solution of 24～28% again;
E) with A) the cellulose pulp small pieces and the D of described desiccated balance) described N-methylmorpholine oxide/carbon black solution is with 5～15: 100 weight ratio joins in the dissolution kettle, after stirring through the brute force of the quiet swelling of 20～40min, 20～60min under 70～90 ℃, be warming up to 90～120 ℃ again, remove moisture through stirring, decompression distillation, the generation moisture is cellulose/N-methylmorpholine oxide/carbon black solution of 12%～14%, the spinning solution of the precursor fiber of the cellulose base carbon fiber of acquisition black.
2. the preparation method of the precursor fiber of cellulose base carbon fiber as claimed in claim 1 is characterized in that:
The temperature of the spinning solution of aforesaid cellulose base carbon fiber precursor fiber is adjusted to 85～100 ℃, through the spinnerets ejection, air gap by 5～300mm, after being the air layer between spinning plate surface and the coagulating bath face, enter pure water or less than solidification forming in 20% the low concentration N-methylmorpholine oxide water solution, after washing, be wound into tube, obtain containing the precursor fiber of the cellulose base carbon fiber of 0.05%～52% carbon black after the drying.
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| CN 200410052885 CN1255585C (en) | 2004-07-15 | 2004-07-15 | Process for preparing precursor fiber of cellulose base carbon fiber |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102102231A (en) * | 2010-12-15 | 2011-06-22 | 福建省纤维检验局 | Method for preparing conductive cellulose fibers |
| CN102788864A (en) * | 2012-06-27 | 2012-11-21 | 中国科学院宁波材料技术与工程研究所 | Method for determining moisture content in polyacrylonitrile polymerized liquid |
| FR2997097A1 (en) * | 2012-10-22 | 2014-04-25 | Arkema France | PROCESS FOR PRODUCING CARBON FIBER, PRECURSOR MATERIAL USED BY THE PROCESS AND CARBON FIBER OBTAINED |
| CN106245131A (en) * | 2016-08-09 | 2016-12-21 | 东华大学 | A kind of precursor fiber preparation method of low-temperature alkaline urea method cellulose base carbon fiber |
| WO2018078288A1 (en) | 2016-10-28 | 2018-05-03 | Arkema France | Method for producing carbon fibres from biosourced precursors and carbon fibres produced |
| WO2018078287A1 (en) | 2016-10-28 | 2018-05-03 | Arkema France | Novel method for producing high-carbon materials and high-carbon material produced |
| FR3075227A1 (en) * | 2017-12-18 | 2019-06-21 | Association Pour Le Developpement De L'enseignement Et Des Recherches Aupres Des Universites, Des Centres De Recherche Et Des Entreprises D'aquitaine (Adera) | PROCESS FOR PRODUCING A CARBON FIBER FROM RECYCLED COTTON AND USING THE FIBER THUS OBTAINED FOR FORMING AN ARTICLE IN COMPOSITE MATERIAL |
| CN111778576A (en) * | 2019-04-03 | 2020-10-16 | 上海水星家用纺织品股份有限公司 | Preparation method of formaldehyde-removing lyocell fibers |
| CN114016141A (en) * | 2021-12-09 | 2022-02-08 | 赛得利(常州)纤维有限公司 | Method for preparing fiber spinning solution by direct dissolution method |
-
2004
- 2004-07-15 CN CN 200410052885 patent/CN1255585C/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102102231A (en) * | 2010-12-15 | 2011-06-22 | 福建省纤维检验局 | Method for preparing conductive cellulose fibers |
| CN102102231B (en) * | 2010-12-15 | 2013-02-06 | 福建省纤维检验局 | Method for preparing conductive cellulose fibers |
| CN102788864A (en) * | 2012-06-27 | 2012-11-21 | 中国科学院宁波材料技术与工程研究所 | Method for determining moisture content in polyacrylonitrile polymerized liquid |
| CN102788864B (en) * | 2012-06-27 | 2015-06-17 | 中国科学院宁波材料技术与工程研究所 | Method for determining moisture content in polyacrylonitrile polymerized liquid |
| FR2997097A1 (en) * | 2012-10-22 | 2014-04-25 | Arkema France | PROCESS FOR PRODUCING CARBON FIBER, PRECURSOR MATERIAL USED BY THE PROCESS AND CARBON FIBER OBTAINED |
| WO2014064373A1 (en) * | 2012-10-22 | 2014-05-01 | Arkema France | Method for manufacturing a carbon fibre, precursor material used by the method and carbon fibre obtained |
| CN104755661A (en) * | 2012-10-22 | 2015-07-01 | 阿克马法国公司 | Method for manufacturing a carbon fibre, precursor material used by the method and carbon fibre obtained |
| CN104755661B (en) * | 2012-10-22 | 2017-04-26 | 阿克马法国公司 | Method for manufacturing a carbon fibre, precursor material used by the method and carbon fibre obtained |
| US9909235B2 (en) | 2012-10-22 | 2018-03-06 | Arkema France | Method for manufacturing a carbon fibre, precursor material used by the method and carbon fibre obtained |
| CN106245131A (en) * | 2016-08-09 | 2016-12-21 | 东华大学 | A kind of precursor fiber preparation method of low-temperature alkaline urea method cellulose base carbon fiber |
| WO2018078288A1 (en) | 2016-10-28 | 2018-05-03 | Arkema France | Method for producing carbon fibres from biosourced precursors and carbon fibres produced |
| WO2018078287A1 (en) | 2016-10-28 | 2018-05-03 | Arkema France | Novel method for producing high-carbon materials and high-carbon material produced |
| CN110062825A (en) * | 2016-10-28 | 2019-07-26 | 阿科玛法国公司 | Prepare high-carbon material new method and prepared high-carbon material |
| US10844521B2 (en) | 2016-10-28 | 2020-11-24 | Arkema France | Process for producing carbon fibres from biosourced precursors and the carbon fibres obtained |
| US11214523B2 (en) | 2016-10-28 | 2022-01-04 | Arkema France | Process for producing highly carbonaceous materials and the highly carbonaceous material obtained |
| FR3075227A1 (en) * | 2017-12-18 | 2019-06-21 | Association Pour Le Developpement De L'enseignement Et Des Recherches Aupres Des Universites, Des Centres De Recherche Et Des Entreprises D'aquitaine (Adera) | PROCESS FOR PRODUCING A CARBON FIBER FROM RECYCLED COTTON AND USING THE FIBER THUS OBTAINED FOR FORMING AN ARTICLE IN COMPOSITE MATERIAL |
| WO2019122648A1 (en) * | 2017-12-18 | 2019-06-27 | Association Pour Le Développement De L'enseignement Et Des Recherches Auprès Des Universités, Des Centres De Recherche Et Des Entreprises D'aquitaine (Adera) | Method for producing a carbon fibre from recycled cotton and use of the fibre obtained in this way for forming an article made from composite material |
| CN111936680A (en) * | 2017-12-18 | 2020-11-13 | 阿基坦大学、研究中心和企业教学和研究发展协会 (Adera) | Method for producing carbon fibres from recycled cotton and use of the fibres thus obtained for forming articles made of composite material |
| US11578433B2 (en) | 2017-12-18 | 2023-02-14 | Association Pour Le Développement De L'enseignement Et Des Recherches Auprès Des Universitès. Des Centres De Recherche Et Des Entreprises D'aqitaine (Adera) | Method for producing a carbon fibre by recycling cotton |
| CN111778576A (en) * | 2019-04-03 | 2020-10-16 | 上海水星家用纺织品股份有限公司 | Preparation method of formaldehyde-removing lyocell fibers |
| CN114016141A (en) * | 2021-12-09 | 2022-02-08 | 赛得利(常州)纤维有限公司 | Method for preparing fiber spinning solution by direct dissolution method |
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| CN1255585C (en) | 2006-05-10 |
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