CN103233298B - Preparation method for high-carbon-content carbon fiber - Google Patents
Preparation method for high-carbon-content carbon fiber Download PDFInfo
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- CN103233298B CN103233298B CN201310167471.7A CN201310167471A CN103233298B CN 103233298 B CN103233298 B CN 103233298B CN 201310167471 A CN201310167471 A CN 201310167471A CN 103233298 B CN103233298 B CN 103233298B
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Abstract
The invention relates to a preparation method for high-carbon-content carbon fiber. The method comprises the steps of: preparing polyacrylonitrile fiber by taking polyacrylonitrile as raw materials through using an electrostatic spinning method; then, placing the polyacrylonitrile fiber into a mixed solution of acetone, dibenzoyl peroxide (BPO), styrene and an antioxidant, radiating for 40minutes under a high-pressure mercury lamp, to obtain polyacrylonitrile-grafted styrene fiber; and finally, carrying out high-temperature carbonization to obtain the needed high-carbon-content carbon fiber. Through scanning electron microscope and element analysis as well as conductive property tests, the carbon content of the high-carbon-content carbon fiber can be improved to 99.46% compared with carbon content of the carbon fiber without ultraviolet grafting, the conductive property can be improved to 5.5ohm.cm<2>, thus proving that the ultraviolet grafting is a potential method for improving the carbon content of the carbon fiber. According to the preparation method, the carbon content of the carbon fiber can be increased, and the conductive property of the carbon fiber can be improved, thus having certain creativity and practicability.
Description
Technical field
The present invention relates to a kind of preparation method of carbon fiber, particularly a kind of polyacrylonitrile utilizes electrostatic spinning, is prepared the method for high-carbon-content carbon fiber after ultraviolet irradiation grafting by pre-oxidation carbonization technique.
Background technology
Carbon fiber changes into the DIC fiber [1] of phosphorus content more than 90% by artificial or synthetic fiber through pre-oxidation carbonization.(JB Tang nanotesla, RC Ban Saer. Carbon fibe [M]. Beijing: Science Press, 1989.1) carbon fiber obtained by the vapor growth method of the charing of the solid phase of macromolecule organic fiber or low molecular hydrocarbon usually.Organic fiber includes viscose glue, polyacrylonitrile-radical and polyimides etc., mainly based on polyacrylonitrile-radical.Along with China's industry, national defence, military development, the composite of carbon fiber and carbon fiber is with its light weight, high comprehensive performance, as the substitute of the metals such as iron and steel, applied to more and more widely in many fields such as chemical industry, electromechanics, shipbuilding, medicine, sports apparatus, communications and transportation, mining, building industry.
The change of carbon element content directly can have influence on the change of carbon fiber chemical constitution, the room stayed after such as atom removes, the change of chemical bond and the restructuring etc. of carbon backbone structure, thus has an impact to the performance of carbon fiber.(research of a new .PAN base carbon fibre microstructure features. Beijing University of Chemical Technology. Master's thesis, 2008.)
The carbon fiber of high carbon content, receives much attention because it has better mechanical performance, heat resistance and better electric conductivity.Scientists diverse ways and means realize the raising of carbon fiber phosphorus content for this reason.
Korea Spro laughs at and coal tar pitch is prepared high-carbon-content carbon fiber 1000 DEG C of high-temperature process, and its phosphorus content can reach 96.56%.(Korea Spro laughs at. the UV absorber of coal tar pitch base carbon fibre. and Anhui University of Science and Technology Master's thesis .2011)
Liu Jianhong etc. adopt free radical polymerisation process to prepare liquid polypropylene nitrile oligomer, obtained the polyacrylonitrile with circulus of high-carbon content, be mixed with sizing agent by thermal oxidation.By polyacrylol oligomer liquid sizing agent impregnation of carbon fibers (carbonization silk) separately or after mixing, heat-treat under the process conditions such as uniform temperature, atmosphere, obtain the high-performance carbon fibre that carbon content is higher.([P]. Chinese patent: CN102212965A, 2010)
Zhang Xiaodongs etc. are by preoxidized polyacrylonitrile precursor high temperature cabonization to 1350 DEG C, and the phosphorus content adopting VARIO Micro cube elemental analyser Dynamic Burning method to record carbon fiber is 94%.(Zhang Xiaodong etc. high temperature cabonization temperature is on the impact of carbon fiber performance. and innovation drives; Accelerate emerging strategic industries development---the 7th, Jilin Province science and technology academic nd Annual Meeting collection .2012)
Polyimide precursor high-temperature process to 1000 DEG C, by FEI Sirion200 type field emission scanning electron microscope test phosphorus content, is obtained the carbon fiber of 96.16% phosphorus content by Zhang Yujun etc.(Zhang Yujun etc. the preparation of ultrafine carbon fiber felt and pattern research thereof. [J] chemistry and bonding .2009,31:25 ~ 28)
He Fu etc. have prepared the polyacrylonitrile-based carbon fibre of 92% phosphorus content by high temperature carbonization furnace, and have studied the impact of retort on carbon fiber forming.(He Fu etc. produce key equipment--the carbide furnace of carbon fiber. [J] tec fiber and application, 2006,31:16 ~ 24)
Hao Jiaxun etc. test the phosphorus content of T300 carbon fiber by carbon and sulfur automatic analyzer, find that its mean value is 92.55%.(Hao Jiaxun etc. the analysis of carbon in carbon fiber. metallurgical analysis, 1995,15:59 ~ 60)
The toray carbon fiber finished product VAEIO EL 111 type elemental analyser that buys to characterize its carbon content, be found that the phosphorus content of M40J carbon fiber is up to 99.57% by Zhang Xin etc., and the compactness of fiber is better, modulus and intensity larger.(research of a new .PAN base carbon fibre microstructure features. Beijing University of Chemical Technology. Master's thesis, 2008.)
In existing research, people are more by improving precursor quality, improving pre-oxidation and carbonization technique etc. to reducing the formation of fault of construction.Improve carbon fiber carbon content, improve its performance.
Electrostatic spinning technique is that polymer solution or melt spray, stretch and obtain the spinning process of nano-scale fiber under electrostatic field.The method just occurred as far back as 20 beginnings of the century.This spining technology has much exclusive characteristic, and the material that it is suitable for is very extensive, and many polymer solutions and melt all can use.This spining technology has become the focus being applied to exploitation superfine nano fiber, and has opened up the potential application of nanofiber.Can be applicable to filtration, obstruct, separation, bio-medical material and dress materials etc. with the nanometer product that electrostatic spinning technique is produced.Adopt electrospinning process also various discrete nano-substance (CNT, ceramic powder etc.) can be spun into continuity fiber, obtain the functional material of excellent performance.(Ko.F et al. Electrospinning of continuous carbon nantube-filled nanofiber yarns[J]. Advanced Materials， 2003， 15：1161~1165)
Radiation processing technology starts from nineteen fifty-two Charlesby discovery irradiation crosslinkable polyolefin material in the application of chemical field, to have occurred again subsequently by irradiation monomer-grafted, on polymer, being made the technology such as initiating accident sequence trigger monomer polymerization by irradiation.(Charlesby A. Proc R Soc, 1952, A215:184 ~ 187) do not have harsh requirement to the form of material, irradiation temperature due to irradiation technique, and reaction is fast, product purity is high, easy to control, practicable continued operation.Therefore irradiation processing industry is considered to a kind of high financial profit, economize energy, saving manpower, nuisanceless or few public hazards method.Ultraviolet irradiation is a kind of in electron beam irradiation.
Its phosphorus content improves by 2500 DEG C of high-temperature process in Xin Mou new science and technology development corporation, Ltd., prepares the carbon fiber that phosphorus content is 96%.Its drawback is that treatment temperature is too high, consumes energy larger.(Xin Mou new science and technology development corporation, Ltd., [Z]. national science and technology achievement. 2004).
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high-carbon-content carbon fiber.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for high-carbon content carbon fiber, is characterized in that the concrete steps of the method are:
A. polyacrylonitrile is dissolved in N-N dimethylacetylamide, is mixed with the spinning solution that concentration is 11wt% ~ 13wt%, adopt method of electrostatic spinning, prepare polyacrylonitrile fibre felt; The electrostatic spinning process parameter adopted is: electrostatic potential is 10 kV ~ 13kV, needle diameter 0.6mm ~ 1.0mm, receiving range 10cm ~ 14cm, and temperature is room temperature, and relative humidity is 55%RH ~ 65%RH;
The fibrofelt of step a gained is immersed in by the mixing acetone soln of peroxidating class initator (0.1mol/L), styrene (1mol/L) and antioxidant (0.1g/L) by b, the concentration of wherein peroxidating class initator is 0.1mol/L, cinnamic concentration is 1mol/L, and the concentration of antioxidant is 0.1g/L; Under high-voltage mercury lamp, irradiate 20min ~ 40min obtain polyacrylonitrile graft styrene fiber;
C. step b gained polyacrylonitrile graft styrene fiber is risen to 250 DEG C ~ 270 DEG C with the heating rate of 5 DEG C/min ~ 10 DEG C/min from room temperature, constant temperature 20min ~ 40min, again under an inert atmosphere, 900 DEG C ~ 1600 DEG C are risen to from 270 DEG C with the heating rate of 10 DEG C/min ~ 20 DEG C/min, constant temperature 1 hour, be cooled to room temperature, namely obtain high-carbon content carbon fiber.
Above-mentioned peroxidating class initator is: dibenzoyl peroxide, methyl ethyl ketone peroxide, peroxidized t-butyl perbenzoate, isopropyl benzene hydroperoxide or cumyl peroxide.
Above-mentioned antioxidant is respectively: antioxidant 1010, sodium metaperiodate or ferrous sulfate.
The present invention is characterized its pattern and phosphorus content by ESEM, and tests its sheet resistance with universal meter.Method described in this patent can reduce the energy consumption of preparation high-carbon-content carbon fiber greatly, and gained carbon fiber phosphorus content is higher.
The present invention utilizes electrostatic spinning and ultraviolet irradiation grafting to prepare high-carbon-content carbon fiber, has high-specific surface area, high carbon content, facilitates carbon fiber in conduction, have more best performance.Tool of the present invention has the following advantages:
A) preparation technology is simple;
B) carbon fiber diameter prepared is thinner;
C) carbon fiber guiding electrical property is better;
D) high-carbon-content carbon fiber has high strength, high temperature resistant, resistance to chemical attack characteristic.
Detailed description of the invention
Embodiment one: the present embodiment concrete steps are:
A. be raw material with polyacrylonitrile, N-N dimethylacetylamide is solvent, mass percent is adopted to be the polyacryl-nitrile spinning fluid of 13%, at room temperature, spinning voltage 13kV, receiving range 14cm between receiving system and spinning head, needle diameter 1.0mm, prepares polyacrylonitrile fibre by electrostatic spinning.
B. polyacrylonitrile fibre is put into acetone, dibenzoyl peroxide (BPO), in the mixed solution of styrene and antioxidant, under high-voltage mercury lamp, irradiate 40min obtain polyacrylonitrile graft styrene fiber.
C. gained graft fibres are risen to 270 DEG C with the heating rate of 5 DEG C/min from room temperature in air dry oven; constant temperature 20min; fiber is being put into high temperature carbonization furnace; 1600 DEG C are risen to from 270 DEG C under nitrogen protection with the heating rate of 20 DEG C/min; constant temperature 1 hour; be cooled to room temperature, take out sample.
Test high-carbon-content carbon fiber phosphorus content and electric conductivity concrete steps are:
A carbon fiber after heat treatment is cut into the square of 2cm*2cm by (), sample is placed in tungsten filament ESEM (S-57 type, Jeol Ltd.), the EDS system carried with instrument, tests its phosphorus content.
B carbon fiber after heat treatment is cut into the square of 2cm*2cm by (), test its conductance with universal meter (VC890D, Shenzhen high Electronic Science and Technology Co., Ltd. of triumph).
Table 1: the electric conductivity of different carbon content carbon fiber
| Percent grafting (%) | Antioxidant | Phosphorus content (%) | Area resistance (Ω .cm2) |
| 0 | Nothing | 95.0 | 98.3 |
| 23.90 | Antioxidant 1010 | 99.46 | 5.5 |
| 6.84 | Ferrous sulfate | 96.54 | 50.6 |
| 8.33 | Sodium metaperiodate | 98.28 | 23.4 |
With the phosphorus content of the carbon fiber of non-grafting process and electric conductivity after (c) contrast grafting process, as shown in table 1, with antioxidant 1010 as antioxidant, phosphorus content after grafting is elevated to 99.46%, electric conductivity also has obvious lifting, show the carbon fiber can being prepared high carbon content by electrostatic spinning ultraviolet irradiation grafting after-baking, and improve its electric conductivity.
Claims (3)
1. a preparation method for high-carbon content carbon fiber, is characterized in that the concrete steps of the method are:
A. polyacrylonitrile is dissolved in N-N dimethylacetylamide, is mixed with the spinning solution that concentration is 11wt% ~ 13wt%, adopt method of electrostatic spinning, prepare polyacrylonitrile fibre felt; The electrostatic spinning process parameter adopted is: electrostatic potential is 10 kV ~ 13kV, needle diameter 0.6mm ~ 1.0mm, receiving range 10cm ~ 14cm, and temperature is room temperature, and relative humidity is 55%RH ~ 65%RH;
The fibrofelt of step a gained is immersed in by the mixing acetone soln of peroxidating class initator, styrene and antioxidant by b, and the concentration of wherein peroxidating class initator is 0.1mol/L, and cinnamic concentration is 1mol/L, and the concentration of antioxidant is 0.1g/L; Under high-voltage mercury lamp, irradiate 20min ~ 40min obtain polyacrylonitrile graft styrene fibrofelt;
C. step b gained polyacrylonitrile graft styrene fibrofelt is risen to 250 DEG C ~ 270 DEG C with the heating rate of 5 DEG C/min ~ 10 DEG C/min from room temperature, constant temperature 20min ~ 40min, again under an inert atmosphere, 900 DEG C ~ 1600 DEG C are risen to from 270 DEG C with the heating rate of 10 DEG C/min ~ 20 DEG C/min, constant temperature 1 hour, be cooled to room temperature, namely obtain high-carbon content carbon fiber.
2. the preparation method of high-carbon content carbon fiber according to claim 1, is characterized in that described peroxidating class initator is: dibenzoyl peroxide, methyl ethyl ketone peroxide, peroxidized t-butyl perbenzoate, isopropyl benzene hydroperoxide or cumyl peroxide.
3. the preparation method of high-carbon content carbon fiber according to claim 1, is characterized in that described antioxidant is respectively: antioxidant 1010, sodium metaperiodate or ferrous sulfate.
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| CN104357958A (en) * | 2014-10-27 | 2015-02-18 | 苏州莱特复合材料有限公司 | High-temperature resistant polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN105624925B (en) * | 2015-12-22 | 2017-07-11 | 苏州协泰科技有限公司 | The production technology of filtering material is produced with the fine precursor of itrile group type carbon |
| CN106049054A (en) * | 2016-05-24 | 2016-10-26 | 马鞍山中创环保科技有限公司 | Method for preparing amphoteric antibacterial ion exchange fibers |
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| CN101230540A (en) * | 2008-02-22 | 2008-07-30 | 东南大学 | Antibiotic polymer nano fibre and preparation method thereof |
| CN101597820A (en) * | 2009-06-09 | 2009-12-09 | 东华大学 | A kind of preparation method of polyacrylonitrile-based carbon fibre |
| CN101736411A (en) * | 2008-11-26 | 2010-06-16 | 中国科学院化学研究所 | Method for preparing polyacrylonitrile spinning solution for carbon fiber |
| JP2012219382A (en) * | 2011-04-04 | 2012-11-12 | Toho Tenax Co Ltd | Method for producing precursor fiber bundle of polyacrylonitrile-based carbon fiber, and precursor fiber bundle of polyacrylonitrile-based carbon fiber obtained by using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101230540A (en) * | 2008-02-22 | 2008-07-30 | 东南大学 | Antibiotic polymer nano fibre and preparation method thereof |
| CN101736411A (en) * | 2008-11-26 | 2010-06-16 | 中国科学院化学研究所 | Method for preparing polyacrylonitrile spinning solution for carbon fiber |
| CN101597820A (en) * | 2009-06-09 | 2009-12-09 | 东华大学 | A kind of preparation method of polyacrylonitrile-based carbon fibre |
| JP2012219382A (en) * | 2011-04-04 | 2012-11-12 | Toho Tenax Co Ltd | Method for producing precursor fiber bundle of polyacrylonitrile-based carbon fiber, and precursor fiber bundle of polyacrylonitrile-based carbon fiber obtained by using the same |
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