CN101112980A - Method for preparing nano carbon fibre by using polyacryl-nitrile (PAN) - Google Patents
Method for preparing nano carbon fibre by using polyacryl-nitrile (PAN) Download PDFInfo
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- CN101112980A CN101112980A CNA200710042818XA CN200710042818A CN101112980A CN 101112980 A CN101112980 A CN 101112980A CN A200710042818X A CNA200710042818X A CN A200710042818XA CN 200710042818 A CN200710042818 A CN 200710042818A CN 101112980 A CN101112980 A CN 101112980A
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Abstract
The invention relates to a method used for preparing nano carbon fiber from (PAN, comprising the steps that: (1) polyacrylonitrile (PAN) and polymethylmethacrylate (PMMA) are dried, the mixture of PAN and PMMA is melted together in cosolvent N, N- dimethyl acetamide (DMF) under a temperature of 50 to 60 DEG C; (2) the polymer mixture solution is used in wet spinning and the scattering size of PAN on PMMA is regulated and controlled by adjusting the drafting ratio so as to acquire a PAN/PMMA blend fiber, in which PMMA is in a continuous phase and PAN is in a discrete phase; (3) the bend fiber is pre-oxidized in the air as a nano carbon fiber precursor and then carbonized; pre-oxidization technique: when the temperature is 150 to 300 DEG C, the time is 4.5 to 6 hours, carbonization is carbonized with the protection of N2, heating up speed is 2 to 20 DEG C per minute, when the temperature is 500 to 1200 DEG C, the time is 40 to 90 minutes, and the nano carbon fiber with a diameter of 100 to 1000nm and a length-diameter of 50 to 100um is acquired. The technique of the method is simple and the fiber prepared through the method has even size and high purity, thereby being suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of carbon nano fiber preparation field, particularly a kind of method for preparing carbon nano fiber with polyacrylonitrile (PAN).
Background technology
Carbon fiber be a kind of be raw material with polyacrylonitrile, pitch, viscose fiber etc., the carbon content that makes through preoxidation, carbonization and greying is greater than 90% high-strength, Gao Mo, high-temperature resistant special fiber.Carbon fiber is being brought into play important role in each mainstay industry of national defence, military field and national economy.But the production of world's carbon fiber mainly concentrates on developed countries such as Japan and the United States, English, and also there are produced in small quantities in Korea S and India.China is except Taiwan plastic cement group, other large-scale productions of all also being far from being, and carbon fiber output only accounts for 0.4% of Gross World Product.Nowadays carbon fiber has developed into the infant industry system of independent completion, has been widely used in each field such as military equipment, aerospace, sports equipment, medicine equipment, weaving.
After 20th century the mid-80s, (diameter is 10-500nm to carbon nano fiber, length-to-diameter ratio is the carbon material of 100-500) come out as the newcomer of carbon fiber family, because nanoscale, this based carbon fiber has bigger specific surface area, very high physical strength, excellent conductivity, macrofiber shape structure, excellent chemical stability etc. and coming into one's own.The successful preparation that particularly has the CNT (carbon nano-tube) of similar physical chemical property with it, its potential applied research has obtained many challenging achievements, has more excited the further investigation of people to carbon nano fiber.More and more researchers is explored the application potential of carbon nano fiber as aspects such as support of the catalyst, electrode materials, absorbing material, high-efficiency adsorbent and polymkeric substance strongtheners by the carbon nano fiber of prepared in various methods high quality low price at present.
At present, preparing carbon nano fiber method commonly used has traditional vapor growth method and method of electrostatic spinning, domestic employment application a small amount of patent (patent publication No.: 1258637,1168348,1389606).The chemical vapor-phase growing method is transition metal (Fe, Ni, Co etc.) granules of catalyst absorbs and decomposes hydrocarbon polymer (as benzene, methyl alcohol etc.) molecule, carbon atom is diffused into the sosoloid that forms metal-carbon behind the catalyst surface, and carbon atom is separated out growth and obtained carbon nano fiber or CNT (carbon nano-tube) from oversaturated granules of catalyst subsequently.Make when producing carbon nano fiber in this way, owing to prepare nm-class catalyst particle comparatively difficulty and granules of catalyst skewness, so the carbon nano fiber of the thin diameter of difficult preparation, and have certain carbon black.The electric field spinning is that polymers soln or melt are under the effect of high-voltage DC power supply (several kilovolts or several ten thousand volts), overcome surface tension, form and spray thread, in course of injection, solvent constantly volatilizees, and the effect of effusive unstable and electrostatic force constantly is stretched jet, and jet division phenomenon takes place sometimes, the final diameter that obtains on collector is that tens nanometers arrive several microns fiber, but this method is difficult to realize the industrialization continuous production.
Up to now, there is not to adopt the method for preparing carbon nano fiber with the polyacrylonitrile for the carbon fiber precursor blending method both at home and abroad.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of method of using polyacrylonitrile (PAN) to prepare carbon nano fiber, and this method technology is easy, all even purity height of fiber size of preparation, is fit to suitability for industrialized production.
A kind of method of using polyacrylonitrile (PAN) to prepare carbon nano fiber of the present invention comprises the following steps:
(1) dry polyacrylonitrile (PAN), polymethylmethacrylate (PMMA) are dissolved in cosolvent N by the PAN/PMMA=5-50/95-50 mass ratio with both mixtures, and in the dinethylformamide, the control solvent temperature is 50-60 ℃;
(2) will be set by step (1) mixed with polymers solution wet spinning of obtaining, spinning process is with general wet spinning technology, by adjusting the dispersion size (500-5000nm) of drafting multiple regulation and control PAN in PMMA, obtaining with PMMA is external phase, and PAN is the PAN/PMMA blended fiber (seeing Fig. 1 Fig. 2) of disperse phase;
(3) will be set by step (2) blended fiber carbon fibre precursor of obtaining in air atmosphere, carry out preoxidation, controlled temperature is 150-300 ℃, the residence time is 4.5-6hr; With the fiber after the preoxidation at N
2Carry out carbonization under the protection, the control temperature rise rate is 2-20 ℃/min, and the top temperature of control carbonization is 500-1200 ℃, and the residence time is 40-90min, is cooled to room temperature, promptly obtains final product, and diameter is the carbon nano fiber (Fig. 3) of 100-1000nm.
Described Fibre diameter is 100-1000nm, and part carbon fiber diameter is nano level below 200nm, and major diameter is 50-100,
Described N, dinethylformamide (DMF) is a SILVER REAGENT, reagent one factory in Shanghai produces.
Described polyacrylonitrile (PAN) is that Kingsoft, Shanghai petrochemical industry acrylic fibers company produces.
Described polymethylmethacrylate (PMMA) is produced for Heilongjiang Longxin Chemical Co., Ltd., and model is Lx-025.
Carbonization residue form judgment basis and diameter testing method thereof: adopt JSM-5600LV type scanning electron microscope, the final product that carbonization is made directly sticks on the aluminium specimen holder, with its size of scanning electron microscopic observation and configuration of surface.The result shows, by the fiber that polyacrylonitrile/polymethylmethacrylate co-mixing system wet-spinning makes, final product through preoxidation and carbonization process is the fine-fibered shape, and diameter between 100 to 1000nm, also has the diameter of part fiber to reach below the 200nm greatly.
Technical conceive of the present invention is as follows:
(1) blending method prepares carbon fibre precursor: utilize the wet-spinning technology to prepare conjugate fiber, wherein carbon fiber precursor is a disperse phase, and the thermo-cracking polymkeric substance is a matrix.And, being used for preparing the co-mixing system of carbon nano fiber, carbon fiber precursor must be dispersed in the thermo-cracking superpolymer with the fento form.The pyrolysis superpolymer can not react with carbon fiber precursor, and both must have certain consistency simultaneously, see it is " sea-island " structure from the fibre section, remove extra large structure by carbonization, stay island structure, can prepare superfine carbon fiber like this.
(2) selection of carbon fiber precursor: polyacrylonitrile is the important precursor that is used to produce carbon fiber, and the output of PAN-based carbon fiber occupy the prostatitis of each based carbon fiber ultimate production always, moreover preoxidized polyacrylonitrile and carbonization technique maturation.
(3) selection of pyrolytic polymer: in theory, most of organic polymer all can be used as pyrolytic polymer, consideration will with polyacrylonitrile blended spinning, so pyrolytic polymer must dissolve in the solvent of polyacrylonitrile, and have good spinning fiberizability, select polymethylmethacrylate for this reason.Polymethylmethacrylate is mixed with polyacrylonitrile by suitable addition, is solvent with DMF, leaves standstill 4hr after the dissolving, observes the stability of solution.The result shows, the mixed solution stability of polyacrylonitrile/polymethylmethacrylate better, demixing phenomenon does not appear, therefore at N, polymethylmethacrylate and polyacrylonitrile consistency are good in the dinethylformamide solvent, polymethylmethacrylate can be used as the pyrolytic polymer matrix, with polyacrylonitrile blended, carries out wet-spinning.
The present invention (after the heat, has the superpolymer of the existence of carbon residue to be called as the carbon precursor in inert atmosphere carbon fiber precursor (CPP) and thermolysis superpolymer (TDP) mixing; The superpolymer of carbon-free residue is called as the pyrolysis superpolymer), with melt spinning method with the co-mixing system spinning, and to spin fiber height stretch, carbonizedfibres is removed the thermolysis superpolymer afterwards, can obtain carbon nano fiber.
Advantage of the present invention is that in the carbon fibre precursor that the blending method spinning obtains, disperse phase polyacrylonitrile dispersion size in the matrix polymethylmethacrylate is even, and dispersion size can be controlled by the drafting multiple of adjusting fiber.Therefore for the carbon fiber that finally obtains, can realize requiring to change its diameter, to satisfy the needs of using according to the producer.
Description of drawings
Fig. 1 is the PAN/PMMA co-mixing system.
Fig. 2 is the PAN/PMMA blended fiber.
Fig. 3 is the carbon nano fiber of 100-1000nm for diameter.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Selecting polyacrylonitrile (PAN) for use is carbon fiber precursor, with polymethylmethacrylate (PMMA) is pyrolytic polymer, with N, dinethylformamide is a cosolvent, blend fully dissolving under 55 ℃ condition with PAN/PMMA=30/70, make mixed with polymers solution, wherein polymer concentration is 26%.Leave standstill to deaeration, the mixed with polymers solution for preparing is carried out conventional wet-spinning, the total draft multiple is 2.6, makes blend PAN/PMMA fiber.
The blend PAN/PMMA fiber that spinning is obtained in convection oven, 150-300 ℃ of following preoxidation 4.5hr; With the fiber after the preoxidation at N
2Protection down is heated to 600 ℃ with the temperature rise rate of 10 ℃/min, and constant temperature 60min is cooled to room temperature, obtains final product, and its diameter is the carbon fiber of 400-500nm.
Embodiment 2
Selecting polyacrylonitrile (PAN) for use is carbon fiber precursor, and adopting polymethylmethacrylate (PMMA) is pyrolytic polymer, the co-mixing system of PAN/PMMA=20/80, with N, dinethylformamide is a solvent, dissolves under 55 ℃ temperature condition, makes mixed with polymers solution.Wherein, polymer concentration is 24%.
The mixed with polymers solution for preparing is carried out conventional wet-spinning, and the total draft multiple is 4.2 times.
The fiber that spinning is obtained in convection oven, 150-300 ℃ of following preoxidation 4.5hr; With the fiber after the preoxidation at N
2Protection down is heated to 1000 ℃ with the temperature rise rate of 10 ℃/min, and constant temperature 60min is cooled to room temperature and obtains final product, and its diameter is 100-200nm.
Embodiment 3
Selecting polyacrylonitrile for use is carbon fiber precursor, and the employing polymethylmethacrylate is a pyrolytic polymer, and with N, dinethylformamide is a solvent, dissolves under 55 ℃ temperature condition, makes mixed with polymers solution, and wherein, polymer concentration is 25%.
The mixed with polymers solution for preparing is carried out wet-spinning, and the total draft multiple is 2.5 times.
The fiber that spinning is obtained in convection oven, 150-300 ℃ of following preoxidation 4.5hr; With the fiber after the preoxidation at N
2Protection down is heated to 900 ℃ with the temperature rise rate of 10 ℃/min, and constant temperature 60min is cooled to room temperature and obtains final product, and its diameter is 500-600nm.
Claims (3)
1. one kind prepares the method for carbon nano fiber with polyacrylonitrile (PAN), comprises the following steps:
(1) dry polyacrylonitrile (PAN), polymethylmethacrylate (PMMA) are dissolved in cosolvent N by the PAN/PMMA=5-50/95-50 mass ratio with both mixtures, in the dinethylformamide (DMF), and solvent temperature 50-60 ℃;
(2) with above-mentioned mixed with polymers solution wet spinning, adjust the dispersion size 500-5000nm of drafting multiple regulation and control PAN in PMMA, obtaining with PMMA is external phase, PAN is the PAN/PMMA blended fiber of disperse phase;
(3) blended fiber is carried out preoxidation earlier as the carbon nano fiber precursor in air atmosphere, temperature 150-300 ℃, time 4.5-6hr is then at N
2Protection carbonization down, temperature rise rate 2-20 ℃/min, carbonization temperature 500-1200 ℃, the time is 40-90min, is cooled to room temperature, obtains the carbon nano fiber that diameter is 100-1000nm, major diameter is 50-100.
2. a kind of method for preparing carbon nano fiber with polyacrylonitrile (PAN) according to claim 1.It is characterized in that: described Fibre diameter reaches below the 200nm, is nano level.
3. a kind of method for preparing carbon nano fiber with polyacrylonitrile (PAN) according to claim 1.It is characterized in that: polyacrylonitrile (PAN) molecular mass need reach the requirement of spinning fibre, i.e. 5-8 * 10
4G/mol, polymethylmethacrylate (PMMA) will use the lower extrusion grade product of melting index.
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