CN101985352B - Method for preparing multi-walled carbon nanotubes from phthalocyanine iron polymer by high temperature solid-phase cracking - Google Patents
Method for preparing multi-walled carbon nanotubes from phthalocyanine iron polymer by high temperature solid-phase cracking Download PDFInfo
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Abstract
The invention discloses a method for preparing multi-walled carbon nanotubes from phthalocyanine iron polymer by high temperature solid-phase cracking, belongs to the technical field of nanomaterials, and provides a simple, high-efficiency and low-cost method for preparing the multi-walled carbon nanotubes. The method comprises the following steps of: performing reflux reaction on bisphthalonitrile and an iron-based catalyst in N-methylpyrrolidone solvent to generate a phthalocyanine iron oligomer; heating and curing the phthalocyanine iron oligomer to obtain the phthalocyanine iron polymer; and finally performing the high temperature solid-phase cracking on the phthalocyanine iron polymer under the protection of an inert gas to obtain the multi-walled carbon nanotubes. By using the two iron-based catalysts of carbonyl iron powder and iron nanopowder, the hollow carbon nanotubes and the carbon nanotubes of which the cores are filled with iron nanopowder can be obtained respectively. The multi-walled carbon nanotubes prepared by the method has high purity, uniform tube diameter and length and can be widely applied to the high-technology fields such as various composite materials, microelectronics and the like.
Description
Technical field
The invention belongs to technical field of nano material, relate to the preparation method of carbon nanotube.
Background technology
Nano material is described as the important materials of 21 century, also is expected to be one of four big pillars that constitute following intelligent society.1991; The breadboard electron microscope expert of Japan's NEC Corporation's fundamental research doctor S.Iijima has found some pipes that formed by the coaxial carbon atom of nano level when the settling that graphite cathode discharge back forms; Iijinma with its called after carbon nanotube (CarbonNanotubes, CNTs).Because making up the carbon-carbon bond of carbon nanotube structure is one of the strongest chemical bond of known occurring in nature, so carbon nanotube has high mechanical strength, should be 100 times of steel through calculating its theoretical tensile strength; And density is merely 1/6 of steel; Also have good flexible, be referred to as super fiber, can be used for the enhancing body of advanced composite materials; Process lightweight, high-strength space hawser, exhibit one's skill to the full in the Aeronautics and Astronautics field.Because carbon nanotube all has superior performance in various fields, therefore, the nearly more than ten years also become the focus of subject researchs such as material, physics, chemistry and biology about the research of carbon nanotube.
Difference according to the thickness of pipe of carbon nanotube can be divided into SWCN and multi-walled carbon nano-tubes with carbon nanotube.SWCN is often referred to the carbon nanotube of tube wall mean thickness below 10 nanometers, because the tube wall of this carbon nanotube almost has only the monolayer carbon atomic thickness; Multi-walled carbon nano-tubes is often referred to the carbon nanotube of thickness of pipe more than 10 nanometers.
The method for preparing at present carbon nanotube roughly has: arc process, catalysis method of evaporation, chemical Vapor deposition process (CVD), laser or ion sputtering method or the like; The complex equipments preparation cost is high, preparation temperature is high but these method ubiquities; The carbon nanotube caliber that makes is inhomogeneous; Crystal defect is many, a series of shortcomings such as separation and purification difficult.With the chemical Vapor deposition process is example: chemical Vapor deposition process is under 600-1000 ℃ temperature, is catalyzer with transition metal or its oxide compound of nanoscale, decomposes carbonaceous gas (carbon monoxide, methane, ethene, propylene, benzene etc.) and prepares carbon nanotube.The diameter of the carbon nanotube of this method preparation receives the influence of the composition and the diameter of catalyzer; Its caliber is inhomogeneous usually, and a lot of crystal defects are arranged, and usually bends and is out of shape; Its Guan Zhonghui bag is mingled with the particle of catalyzer; Therefore brought difficulty for follow-up separation and purification, and this method is very high to the production unit requirement, suitable suitability for industrialized production.
Carbon source as the preparation carbon nanotube has carbon monoxide, methane, ethene, propylene, benzene etc. usually, is inorganics or small organic molecule mostly.For example: Institutes Of Technology Of Taiyuan has reported to be that carbon source, Fe and oxide compound thereof are catalyzer, prepare the method for carbon nanotube via arc discharge method with the colour carbon black.This method just can obtain effect preferably under normal pressure, the output of carbon nanotube is higher in the product, but on the tube wall of carbon nanotube, finds more small-particle.Korea Research Institute of Chemical Technology has applied for " method that is prepared carbon nanotube by phase carbon source " (one Chinese patent application number: 200480008689) in 2004; This invention relates to a kind of method of utilizing hydrocarbon liquid phase sill induced carbon nanotube growth in the critical range that is equilibrated between the liquid and gas; Though this method is handled required carbon source with comparalive ease; But this method still needs the growth of metal catalyst with stimulation carbon pipe, and gas-liquid critical condition is difficult to control.Shanghai Inst. of Applied Physics Chinese Academy of Sciences is carbon source with ethanol, under low air pressure condition, in porous alumina formwork, has prepared carbon nano pipe array with chemical vapour deposition technique.High temperature solid-state cracking with low molecular compound prepares the existing report of carbon nanotube; Liming Dai etc. has delivered the research work that is entitled as " Aligned Coaxial Nanowires of Carbon Nanotubes Sheather with ConducingPolymers " on " Angew.Chem.Int.Ed; 2000,39, No.20; p3664 "; Mainly with small molecules phthalocyanine metal compound as carbon source, under argon gas and hydrogen mixed gas concrete conditions in the establishment of a specific crime, 800～1100 ℃ of Pintsch processs obtain the carbon nanotube of trace.More than related carbon source, mostly exist low this shortcoming of carbon yield after the high-temperature roasting, thereby can't guarantee higher productive rate.
Bi-phthalonitrile resin is one type of high performance thermosetting resin by contrast; Its cured article has fabulous heat, oxidative stability; After 800 ℃ of high-temperature roastings, still have the remaining carbon near 70%, this high-performance itself has guaranteed the high transformation efficiency and the productive rate of carbon pipe.
Summary of the invention
The present invention provides the cracking of a kind of FePC polymkeric substance high temperature solid-state to prepare the method for multi-walled carbon nano-tubes; This method is initial carbon source with bis-phthalonitrile monomer; Under solvent refluxing (boiling) condition, generate FePC oligopolymer (or being the FePC prepolymer) with the metal iron particles reaction; The FePC oligopolymer solidify to form the FePC polymkeric substance through heating up, and the FePC polymkeric substance obtains multi-walled carbon nano-tubes through follow-up high temperature solid-state cracking again.
Technical scheme of the present invention is following:
The cracking of a kind of FePC polymkeric substance high temperature solid-state prepares the method for multi-walled carbon nano-tubes, and is as shown in Figure 1, may further comprise the steps:
Step 1: according to 100: the mass ratio of (2～6) takes by weighing bi-phthalonitrile and Fe-series catalyst, and wherein said Fe-series catalyst is carbonyl iron dust (Fe (CO)
5) or nanometer iron powder (Fe).
Step 2: bi-phthalonitrile and Fe-series catalyst that step 1 takes by weighing are put into the back flow reaction container, add the N-Methyl pyrrolidone solvent, heated and stirred refluxed reaction 4～8 hours generates the FePC prepolymer.Wherein the consumption of N-Methyl pyrrolidone solvent is every gram bi-phthalonitrile with 0.8～1.8 milliliter N-Methyl pyrrolidone;
Step 3: step 2 gained FePC prepolymer is separated the oven dry of washing back from reaction soln.
Step 4: the FePC prepolymer intensification after step 3 oven dry is solidified, make FePC prepolymer generation curing cross-linking reaction, obtain the FePC polymkeric substance.The concrete processing condition of FePC prepolymer intensification solidified are: elder generation is incubated 2～6 hours down at 240 ℃～280 ℃, is incubated 2～6 hours down at 260 ℃～300 ℃ then, and insulation was not less than 50 hours under 300 ℃ at last.
Step 5: step 4 gained FePC polymkeric substance is placed atmosphere of inert gases, obtain multi-walled carbon nano-tubes after solid phase scission reaction, the cooling under the high temperature.The concrete processing condition of solid phase scission reaction are under the FePC polymkeric substance high temperature: starting temperature is 300 ℃, and first temperature rise rate with 1～10 ℃/min rises to 340～360 ℃ and is incubated 30 minutes to 2 hours down; Temperature rise rate with 1～10 ℃/min rises to 390～410 ℃ of following insulations 30 minutes to 2 hours then; Temperature rise rate with 1～5 ℃/min rises to 490～510 ℃ of following insulations 3～5 hours again; At last with the temperature rise rate of 1～3 ℃/min rise to 790～800 ℃ down insulation be no more than 8 hours.
The present invention is initial carbon source with bis-phthalonitrile monomer, under solution, generates FePC oligopolymer (as shown in Figure 2) with the metal iron particles reaction, and this reaction is appreciated that and is a kind of complex reaction.The minimum curing cross-linking reaction temperature of FePC prepolymer is 233 ℃; The present invention is arranged to three thermal process reactors with the curing cross-linking reaction process; Wherein 240 ℃～280 ℃ are provided with two insulation points down with under 260 ℃～300 ℃; Its objective is and reduce curing cross-linking reaction speed to improve the quality of FePC polymkeric substance, under 300 ℃, being incubated and being not less than 50 hours is to let the abundant polymerization of FePC prepolymer obtain the FePC polymkeric substance; The curing cross-linking reaction process does not have special demands to heat-up rate.The present invention is arranged to four thermal process reactors with the high temperature solid-state scission reaction process of FePC polymkeric substance; Wherein under 340～360 ℃, 390～410 ℃, 490～510 ℃ and 790～800 ℃, be provided with four insulation points; The heat-up rate of four thermal process reactors is by high step-down; Should slowly heat up during near the fusing point (about 800 ℃) of FePC polymkeric substance, and soaking time can not surpass 8 hours, cave in otherwise embrittlement can take place the carbon nanotube that generates.Kind, pressure and flow to rare gas element in the high temperature solid-state scission reaction process of FePC polymkeric substance do not have particular requirement, actually select cheaply that nitrogen gets final product for use.
The Fe-series catalyst that adopts in the step 1 is carbonyl iron dust (Fe (CO)
5) or nanometer iron powder (Fe), can obtain two kinds of different-shapes respectively, the carbon nanotube of different performance.If adopt carbonyl iron dust (Fe (CO)
5), the carbon nanotube of final preparation is hollow carbon nanotube (as shown in Figure 4); If adopt nanometer iron powder (Fe), the carbon nanotube of final preparation is the carbon nanotube (as shown in Figure 6) that tube core is filled with nanometer iron powder.
The invention has the beneficial effects as follows:
The present invention proposes with bi-phthalonitrile resin as initial carbon source, generated the FePC prepolymer, utilized the FePC polymkeric substance high temperature solid-state scission reaction of FePC prepolymer crosslinking curing gained to prepare the method for multi-walled carbon nano-tubes then by bi-phthalonitrile tree and Fe-series catalyst back flow reaction in the N-Methyl pyrrolidone solvent first.Preparing method of the present invention is simple, and equipment cost is cheap, and maturing temperature is 800 ℃ and is lower than most preparing methods; Adopt rare gas element as shielding gas; Need not feed inflammable gass such as hydrogen or Sweet natural gas, SF is high, owing to the superior thermotolerance of bi-phthalonitrile, high carbon yield; Guaranteed the high production rate of carbon nanotube, these have great significance for the suitability for industrialized production that realizes carbon nanotube.
Description of drawings
Fig. 1 is a schematic flow sheet of the present invention.
Fig. 2 is to be initial carbon source with bis-phthalonitrile monomer among the present invention, under solution, generates the reaction principle of FePC oligopolymer with the metal iron particles reaction.
Fig. 3 is one of carbon nanotube scanning electron microscope diagram of preparing of the present invention.
Fig. 4 is the hollow multi-walled carbon nano-tubes transmission electron microscope figure that the present invention prepares.
Fig. 5 is two of the carbon nanotube scanning electron microscope diagram for preparing of the present invention.
Fig. 6 is the transmission electron microscope figure that tube core that the present invention prepares is filled with the multi-walled carbon nano-tubes of nanometer iron powder.
Embodiment
The cracking of a kind of FePC polymkeric substance high temperature solid-state prepares the method for multi-walled carbon nano-tubes, and is as shown in Figure 1, may further comprise the steps:
Step 1: according to 100: the mass ratio of (2～6) takes by weighing bi-phthalonitrile and Fe-series catalyst, and wherein said Fe-series catalyst is carbonyl iron dust (Fe (CO)
5) or nanometer iron powder (Fe).
Step 2: bi-phthalonitrile and Fe-series catalyst that step 1 takes by weighing are put into the back flow reaction container, add the N-Methyl pyrrolidone solvent, heated and stirred refluxed reaction 4～8 hours generates the FePC prepolymer.
Step 3: step 2 gained FePC prepolymer is separated the oven dry of washing back from reaction soln.
Step 4: the FePC prepolymer intensification after step 3 oven dry is solidified, make FePC prepolymer generation curing cross-linking reaction, obtain the FePC polymkeric substance.The concrete processing condition of FePC prepolymer intensification solidified are: elder generation is incubated 2～6 hours down at 240 ℃～280 ℃, is incubated 2～6 hours down at 260 ℃～300 ℃ then, and insulation was not less than 50 hours under 300 ℃ at last.
Step 5: step 4 gained FePC polymkeric substance is placed atmosphere of inert gases, obtain multi-walled carbon nano-tubes after solid phase scission reaction, the cooling under the high temperature.The concrete processing condition of solid phase scission reaction are under the FePC polymkeric substance high temperature: starting temperature is 300 ℃, and first temperature rise rate with 1～10 ℃/min rises to 340～360 ℃ and is incubated 30 minutes to 2 hours down; Temperature rise rate with 1～10 ℃/min rises to 390～410 ℃ of following insulations 30 minutes to 2 hours then; Temperature rise rate with 1～5 ℃/min rises to 490～510 ℃ of following insulations 3～5 hours again; At last with the temperature rise rate of 1～3 ℃/min rise to 790～800 ℃ down insulation be no more than 8 hours.
Gained FePC prepolymer in the step 2, recording melting range with DSC (DSC) analyser is 220～240 ℃.
Embodiment 1 is a primary carbon source with the bi-phthalonitrile, and carbonyl iron dust is a catalyzer, adopts the solid phase cracking process to prepare carbon nanotube.
1. take by weighing 10 gram bis-phthalonitrile monomers, 0.6 gram carbonyl iron dust, the three-necked bottle of packing into is poured the 15ml N-Methyl pyrrolidone into as solvent; Be warming up to 200 ℃, refluxed 4 hours.
2. solution is poured in the water, filtered, the solid that leaches with deionized water wash 2～3 times, oven dry is collected.
3. the sample of collecting in the step 2 was solidified 50 ℃～4 hours according to follow procedure, 280 ℃～4 hours, 300 ℃～50 hours.
4. feeding nitrogen, then step 3, starting temperature is 300 ℃, rises to 350 ℃ (constant temperature 1 hour) with the temperature rise rate of 5 ℃/min; 5 ℃/min to 400 ℃ (constant temperature 1 hour); 3 ℃/min to 500 ℃ (constant temperature 4 hours); 2 ℃/min to 800 spends (constant temperature 8 hours).
Fig. 4 is the scanning electron microscope diagram of the carbon nanotube that arrives of aforesaid method.The straight carbon nanotube of as can be seen from the figure large-area length generates, and its length is in micron dimension, the about 100nm of caliber.
Fig. 5 is the transmission electron microscope figure of the carbon nanotube that arrives of aforesaid method.As can be seen from the figure, carbon nanotube hollow, beginning, wall thickness is approximately 30nm, about 40 nanometers of internal diameter.And do not find a large amount of nano-scale carbon particles, explain that the carbon nano pipe purity of gained is higher.Recording its volume specific resistance is 1.9 * 10
-2Cm
-1, magnetic saturation intensity is 1.5emu/g.
Embodiment 2 is a primary carbon source with the bi-phthalonitrile, and nanometer iron powder is a catalyzer, adopts the solid phase cracking process to prepare carbon nanotube.
1. take by weighing 10 gram bis-phthalonitrile monomers, 0.2 gram nanometer iron powder, the three-necked bottle of packing into is poured the 15ml N-Methyl pyrrolidone into as solvent.Be warming up to 200 ℃, refluxed 4 hours.
2. solution is poured in the water, filtered, the solid that leaches with deionized water wash 2～3 times, oven dry is collected.
3. the sample of collecting in the step 2 was solidified 50 ℃～4 hours according to follow procedure, 280 ℃～4 hours, 300 ℃～50 hours.
4. feeding nitrogen, then step 3, starting temperature is 300 ℃, rises to 350 ℃ (constant temperature 1 hour) with the temperature rise rate of 5 ℃/min; 5 ℃/min to 400 ℃ (constant temperature 1 hour); 3 ℃/min to 500 ℃ (constant temperature 4 hours); 2 ℃/min to 800 spends (constant temperature 8 hours).
Fig. 5 is the scanning electron microscope diagram of the carbon nanotube that arrives of aforesaid method.The straight carbon nanotube of as can be seen from the figure large-area length generates, and its length is at tens of microns, the about 100nm of caliber.
Fig. 6 is the transmission electron microscope figure of the carbon nanotube that arrives of aforesaid method.As can be seen from the figure, the carbon nanotube wall thickness is approximately 30nm, about 40 nanometers of internal diameter, and tube core is filled with nanometer iron powder (shown in the arrow) more than 90%.Do not find a large amount of nano-scale carbon particles, the carbon nano pipe purity of gained is higher.Recording its volume specific resistance is 2.4 * 10
-2Cm
-1, magnetic saturation intensity is 3.5emu/g.
Should clarifyingly be, the foregoing description be not to be the further qualification that the present invention is done, and those skilled in the art are as long as implement according to technical scheme of the present invention, and it is higher all can to obtain purity, caliber, the uniform multi-walled carbon nano-tubes of length.
Claims (1)
1. FePC polymkeric substance high temperature solid-state cracking prepares the method for multi-walled carbon nano-tubes, may further comprise the steps:
Step 1: according to 100: the mass ratio of (2～6) takes by weighing bi-phthalonitrile and Fe-series catalyst, and wherein said Fe-series catalyst is carbonyl iron dust or nanometer iron powder;
Step 2: bi-phthalonitrile and Fe-series catalyst that step 1 takes by weighing are put into the back flow reaction container, add the N-Methyl pyrrolidone solvent, heated and stirred refluxed reaction 4～8 hours generates the FePC prepolymer; Wherein the consumption of N-Methyl pyrrolidone solvent is every gram bi-phthalonitrile with 0.8～1.8 milliliter N-Methyl pyrrolidone;
Step 3: step 2 gained FePC prepolymer is separated the oven dry of washing back from reaction soln;
Step 4: the FePC prepolymer intensification after step 3 oven dry is solidified, make FePC prepolymer generation curing cross-linking reaction, obtain the FePC polymkeric substance;
The concrete processing condition of FePC prepolymer intensification solidified are: elder generation is incubated 2～6 hours down at 240 ℃～280 ℃, is incubated 2～6 hours down at 260 ℃～300 ℃ then, and insulation was not less than 50 hours under 300 ℃ at last;
Step 5: step 4 gained FePC polymkeric substance is placed atmosphere of inert gases, obtain multi-walled carbon nano-tubes after solid phase scission reaction, the cooling under the high temperature;
The concrete processing condition of solid phase scission reaction are under the FePC polymkeric substance high temperature: starting temperature is 300 ℃, and first temperature rise rate with 1～10 ℃/min rises to 340～360 ℃ and is incubated 30 minutes to 2 hours down; Temperature rise rate with 1～10 ℃/min rises to 390～410 ℃ of following insulations 30 minutes to 2 hours then; Temperature rise rate with 1～5 ℃/min rises to 490～510 ℃ of following insulations 3～5 hours again; At last with the temperature rise rate of 1～3 ℃/min rise to 790～800 ℃ down insulation be no more than 8 hours.
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| CN102336759A (en) * | 2011-07-21 | 2012-02-01 | 首都师范大学 | Preparation method of planar binuclear metal phthalocyanine coordination compound |
| CN102775755B (en) * | 2012-07-31 | 2013-12-11 | 电子科技大学 | Polyaryl ether nitrile (PEN) and carbonyl iron powder (Fe(CO)5) composite magnetic material and preparation method thereof |
| CN103342790B (en) * | 2013-06-24 | 2015-11-18 | 苏州大学 | Preparation method for in-situ synthesis of phthalocyanine polymer |
| CN104327797B (en) * | 2014-10-14 | 2016-03-16 | 中国工程物理研究院化工材料研究所 | A kind of preparation method of partial carbonization FePC wave absorbing agent and gained wave absorbing agent and application thereof |
| CN104555986B (en) * | 2015-01-06 | 2016-06-08 | 武汉大学 | A kind of preparation method of carbon nano-tube based on solid phase pyrolysis |
| CN105836727B (en) * | 2016-03-21 | 2018-10-23 | 陕西师范大学 | A kind of method that low cost prepares multi-walled carbon nanotube |
| CN107286649B (en) * | 2017-08-01 | 2020-03-31 | 四川理工学院 | Electromagnetic microwave shielding composite material and preparation method thereof |
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| CN1424250A (en) * | 2002-12-24 | 2003-06-18 | 西安交通大学 | Process for growing and purifying carbon nano tube by thermolysis with resistor furnace with single temperature zone |
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