CN1257945C - Polymer thin layer coated carbon nanometer tube and its preparation method - Google Patents
Polymer thin layer coated carbon nanometer tube and its preparation method Download PDFInfo
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- CN1257945C CN1257945C CN 200310109074 CN200310109074A CN1257945C CN 1257945 C CN1257945 C CN 1257945C CN 200310109074 CN200310109074 CN 200310109074 CN 200310109074 A CN200310109074 A CN 200310109074A CN 1257945 C CN1257945 C CN 1257945C
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Abstract
The present invention provides a carbon nanometer tube coated by a polymer thin layer and a preparation method thereof. The preparation method comprises: step (a), the carbon nanometer tube and a dense strong oxidation acid are co-boiled to prepare an amphipathic carbon nanometer tube with a modified surface; steps (b), after mixed with a polymer with the corresponding proportion, the amphipathic carbon nanometer tube in the step (a) is dispersed into one solvent; steps (c), the other immiscible solvent is added, and is stood after treated by ultrasonic waves, and carbon nanometer tube samples on an interface are collected so as to obtain the carbon nanometer tube coated by a polymer thin layer. The preparation method has the advantages of simplicity, practicality and high coating efficiency. On the basis of maintaining the original intensity and the mechanical property of the carbon nanometer tube, the surface property is changed. One layer of polymers with nanometers of thicknesses are uniformly coated on the surface of the obtained carbon nanometer tube. The carbon nanometer tube coated by a polymer thin layer can be used as a super capacitor or nanometer devices, such as nanometer cables, etc., and has wide application prospects.
Description
Technical field: the present invention relates to a kind of preparation method of carbon nano tube device, particularly polymer foil enveloped carbon nanometer tube and preparation method thereof.
Background technology: carbon nanotube (Cabon Nanotube is called for short CNT) is just found a kind of novel carbon structure in 1991, is the body that is rolled into by the Graphene lamella that carbon atom forms.Carbon nanotube be divided into Single Walled Carbon Nanotube (Single-wall Nanotube, SWNT) and multi-walled carbon nano-tubes (Multi-wall Nanotube, MWNT).Its preparation method mainly contains catalyse pyrolysis, arc-over, template and laser evaporation etc.
Because diameter is very little, length-to-diameter ratio is big, carbon nanotube is regarded as quasi-one-dimensional nanometer material.Confirmed now that carbon nanotube has peculiar electric property, superpower mechanical property, good adsorption property, thereby caused very big attention in the material field.The transistor and the indicating meter that have now had carbon nanotube to make come out.
Along with the development of nano science and technology, various carbon nanotubes with specified property cause people's interest gradually.The acid treatment that people such as Richard E.Smalley scrutinized carbon nanotube in 1998, obtained the products distribution situation under the different treatment condition, this has laid good basis (Science, 1998,280 (22): 1253-1255) for further studying later on.Afterwards, various modified carbon nano-tubes and composite structure thereof are produced out.Such as carbon nanotube with solvent solubility, have carbon nano tube device of molecular detection function or the like.
Carbon nanotube/high molecule nano composite material obtains exploitation owing to having excellent performance.The preparation of carbon nanotube/high molecule nano composite material generally is divided into dual mode, a kind of be with the CNT (carbon nano-tube) mechanical dispersion in high molecular polymer, be called " blend "; Another kind of mode is after functional group is gone up in carbon nano tube surface processing connection, to carry out in-situ polymerization, thereby obtain connecting carbon nanotube/high molecule nano composite material by covalent linkage.
Above complex method just lays particular emphasis on the strongthener of carbon nanotube as polymkeric substance is used, and does not notice the polymer foil composite carbon nanometer tube as this direction of nano-device, and the preparation process relative complex.And the polymer foil enveloped carbon nanometer tube has the performance that is different from the carbon nanotube body, thereby has different ranges of application.
Summary of the invention:
The present invention relates to a kind of carbon nano tube device, particularly polymer foil coated carbon nanotube device.
By molecular designing, carbon nano tube surface is handled, make it to have the amphiphilic performance, thereby can all have affinity interaction polarity and apolar substance; When carbon nanotube is added the solution of polymkeric substance, because the extremely strong adsorptive power of carbon nanotube itself, the one layer of polymeric molecule is adsorbed on the carbon nanotube, but this process has reversibility, from macromolecular solution, take out carbon nanotube later on not the homogeneous polymer thin layer be coated to polymer surfaces, when adding another kind of inconsistent solvent, through mechanical oscillation, amphipathic carbon nanotube will be gathered in two-phase interface, polymer molecule can only be wrapped on the carbon nanotube, forms the polymer foil coated carbon nanotube.
Technical scheme of the present invention is as follows:
The present invention at first prepares amphipathic carbon nanotube, select two kinds of solvents that can not dissolve each other then, carbon nanotube is dissolved in or is scattered in wherein one mutually with polymkeric substance, treat basicly stable after, add another kind of solvent, obtain the interface, wait carbon nanotube to gather after the interface, collect, obtain product.
The preparation method of the hyperbranched enveloped carbon nanometer tube of the present invention is specific as follows:
Step (a): 1 weight part (quality, exsiccant carbon nanometer tube material and 0.1～100 weight part acid with strong oxidizing property down together), with 0～100kHz ultrasonication, 0.1～100hr post-heating to 20～200 ℃, reaction 0.5～100hr, with the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains amphiphilic carbon nano tubes behind 0～180 ℃ of vacuum-drying 10～30hr;
Step (b): 1 weight part step (a) gained amphiphilic carbon nano tubes with after 0.1～100 parts by weight polymer is mixed, is distributed in a kind of solvent, and polymkeric substance can well dissolving in this solvent;
Step (c): the immiscible solvent of solvent for use in another kind and the step (b) is joined step (b) gained system, standing demix behind ultrasonication 0.1～100hr, collect the carbon nanotube sample on the interface, after the solvent cleaning with the soluble polymeric thing, drying obtains the carbon nanotube of polymer overmold.
Used carbon nanotube is the single wall or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template and the preparation of laser evaporation method in the inventive method step (a).
Used acid with strong oxidizing property comprises 0.1～70% weight acid concentration nitric acid, 0.1～100% weight acid concentration sulfuric acid, 1/100～100/1 mol ratio nitric acid and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and hydrochloric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and nitric acid mixing solutions, 1/100～100/1 mol ratio H in the inventive method step (a)
2O
2With sulfuric acid mixed solution, 1/100～100/1 mol ratio H
2O
2With hydrochloric acid mixed solution, 1/100～100/1 mol ratio H
2O
2With the nitric acid mixing solutions.
Used polymkeric substance comprises polyolefine, polyacrylic, polystyrene type and polyamide polymers, particularly polyethylene, polypropylene, polybutene, polystyrene, poly-sulfonated phenylethylene, polyvinyl chloride, polymethylmethacrylate, polymethyl acrylate, polyhutadiene, polyethyl acrylate, polyacrylamide and composition thereof in the inventive method step (b).
Solvent for use is water, dimethyl sulfoxide (DMSO), N among the inventive method step (b), (c), dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), ethyl acetate, acetone, butanone, acetonitrile, propyl alcohol, ethanol, methyl alcohol or contain the mixture of these solvents.
The covering amount of polymer foil enveloped carbon nanometer tube is measured through thermogravimetric analysis.The pattern of polymer foil enveloped carbon nanometer tube confirms that through digital photograph and transmission electron microscope it the results are shown in accompanying drawing.
Polymer foil enveloped carbon nanometer tube prepared according to the methods of the invention, preparation technology is simple, the products obtained therefrom polymer overmold is even, and is suitable to extraordinary nano-device such as super capacitor etc., has a wide range of applications in fields such as electronics.
Description of drawings:
Fig. 1: amphiphilic carbon nano tubes accumulates in the photo of two-phase interface
Fig. 2: the transmission electron microscope photo of polymethylmethacrylate (PMMA) enveloped carbon nanometer tube
Embodiment: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: the multiple-wall carbon nanotube with the catalytic pyrolysis method preparation is an initial raw material, carry out azeotropic with concentrated nitric acid and handle, make the surface have the hydrophilic functional group, because the lipophilicity of carbon nanotube body, such carbon nanotube just has amphipathic, can disperse in different solvents.Then polymethylmethacrylate is made into chloroformic solution, add a small amount of amphipathic carbon nanotube, after stirring for some time, add the deionized water of certain volume again, carry out the fierceness vibration, make two-phase contact as far as possible, leave standstill layering then, when gathering two-phase interface Deng carbon nanotube, collect product,, obtain the polymethylmethacrylate coated carbon nanotube with methanol wash and dry.
Step (a): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add 2g exsiccant carbon nanometer tube material and 20mL 60% nitric acid, with 40kHz ultrasonication 30min post-heating to 120 ℃, reaction 24hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain amphiphilic carbon nano tubes 1.5g behind 80 ℃ of vacuum-drying 24hr with the deionized water repetitive scrubbing;
Step (b): take by weighing 1g polymethylmethacrylate (PMMA, M
n=10,000, M
w/ M
n=1.45) join in the Boiling tube, and add chloroform 20mL, dissolving back adding amphiphilic carbon nano tubes 0.05g, maintenance 2hr is down stirred in fierce vibration;
Step (c): add deionized water 20mL, standing demix behind fierce vibration and the supersound process 10min is collected the carbon nanotube sample on the interface, and after washed with methanol, drying obtains the carbon nanotube of polymer overmold.
The result is with TGA and tem analysis.TGA result such as table 1.
Table 1
| Sample | Weightless situation | 300～400 ℃ of weight loss % |
| Former carbon nanotube | Do not have weightless to 650 ℃ | 0 |
| Amphiphilic carbon nano tubes | 650 ℃ have a small amount of weightlessness | 3％ |
| The PMMA enveloped carbon nanometer tube | 330～400 ℃ have obvious weightlessness | 20％ |
Embodiment 2: the multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is a raw material, coats polystyrene.
Remove polymkeric substance and change polystyrene (PS, M into
n=13,000, M
w/ M
n=1.50) outside, all prepare the polystyrene coated carbon nanotube by aforesaid preparation process.TGA analytical results such as table 2.
Table 2
| Sample | Weightless situation | 350～450 ℃ of weight loss % |
| Former carbon nanotube | Do not have weightless to 650 ℃ | 0 |
| Amphiphilic carbon nano tubes | 650 ℃ have a small amount of weightlessness | 3％ |
| The PS enveloped carbon nanometer tube | 350～450 ℃ have obvious weightlessness | 24％ |
Claims (3)
1. the preparation method of polymer foil enveloped carbon nanometer tube is characterized in that the preparation method is as follows:
Step (a): 1 weight part exsiccant carbon nanotube and 0.1～100 weight part acid with strong oxidizing property, with 0.1～100kHz ultrasonication, 0.1～100hr post-heating to 20～200 ℃, reaction 0.5～100hr, use the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains amphiphilic carbon nano tubes behind 0～180 ℃ of vacuum-drying 10～30hr; Wherein acid with strong oxidizing property is selected from 0.1～70wt% nitric acid, 0.1～100wt% sulfuric acid, 1/100～100/1 mol ratio nitric acid and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and hydrochloric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and nitric acid mixing solutions, 1/100～100/1 mol ratio hydrogen peroxide and sulfuric acid mixed solution, 1/100～100/1 mol ratio hydrogen peroxide and hydrochloric acid mixed solution or 1/100～100/1 mol ratio hydrogen peroxide and nitric acid mixing solutions;
Step (b): 1 weight part step (a) gained amphiphilic carbon nano tubes with after 0.1～100 parts by weight polymer is mixed, is distributed in a kind of solvent, and polymkeric substance can well dissolving in this solvent; Wherein polymkeric substance is selected from polyethylene, polypropylene, polybutene, polystyrene, poly-sulfonated phenylethylene, polyvinyl chloride, polymethylmethacrylate, polymethyl acrylate, polyhutadiene, polyethyl acrylate, polyacrylamide or its mixture; Solvent is selected from water, dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), ethyl acetate, acetone, butanone, acetonitrile, propyl alcohol, ethanol, methyl alcohol or its mixed solvent;
Step (c): the immiscible solvent of solvent for use in another kind and the step (b) is joined step (b) gained system, standing demix behind ultrasonication 0.1～100hr, collect the carbon nanotube sample on the interface, after the solvent cleaning with the soluble polymeric thing, drying obtains the carbon nanotube of polymer overmold; Wherein solvent is selected from water, dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), ethyl acetate, acetone, butanone, acetonitrile, propyl alcohol, ethanol, methyl alcohol or its mixed solvent.
2. the preparation method of polymer foil enveloped carbon nanometer tube according to claim 1 is characterized in that used carbon nanotube is selected from single wall or the multi-walled carbon nano-tubes that catalyse pyrolysis, arc-over, template or laser evaporation method prepare in the step (a).
3. the polymer foil coated carbon nanotube is characterized in that the polymer foil coated carbon nanotube that adopts each described preparation method of claim 1-2 to obtain.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1306203C (en) * | 2005-03-18 | 2007-03-21 | 四川大学 | Multiplayer composite tube made from polymer possessing texture in nano layer and making method |
| CN101327415B (en) * | 2008-07-24 | 2012-10-03 | 中国科学院上海硅酸盐研究所 | Dispersing method of polyalcohol dispersing agent of one-dimensional carbon nano material |
| CN102167912A (en) * | 2011-02-22 | 2011-08-31 | 徐州师范大学 | Method for improving dispersity of carbon nano tube in water and water-soluble polymer |
| CN102515141B (en) * | 2011-12-02 | 2015-03-25 | 东华理工大学 | Method for synthesizing modified SWCNTs (Single Wall Carbon Nano Tubes) based on Bergman cyclizing reaction |
| CN104130753A (en) * | 2014-07-15 | 2014-11-05 | 西南科技大学 | High-thermal-conductivity high-electrical-conductivity carbon nano-grade composite material and preparation method thereof |
| CN106957540B (en) * | 2017-03-05 | 2018-12-25 | 北京工业大学 | A kind of method of effective dispersing Nano carbon tubes |
| CN107986258A (en) * | 2017-12-12 | 2018-05-04 | 东华大学 | A kind of regulation and control method of the pore structure of carbon nano-tube film |
| CN108049166A (en) * | 2017-12-12 | 2018-05-18 | 东华大学 | A kind of preparation method of multifunctional carbon nanotube complex yarn |
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